JP5949779B2 - Benzofluorene compound, light emitting layer material and organic electroluminescent device using the compound - Google Patents

Description

  The present invention relates to a benzofluorene compound, a light emitting layer material using the compound, and an organic electroluminescent device.

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

  An organic electroluminescent element has a structure which consists of a pair of electrode which consists of an anode and a cathode, and the one layer or several layer which is arrange | positioned between the said pair of electrodes and contains an organic compound. The layer containing an organic compound includes a light-emitting layer and a charge transport / injection layer that transports or injects charges such as holes and electrons, and various organic materials have been developed as the organic compound (for example, International Publication No. 2004/061047, International Publication No. 2004/061048 (Special Table No. 2006-512395), International Publication No. 2005/056633 (see Patent Documents 1, 2, and 3).

  However, only the polymer compound of benzofluorene is disclosed in the examples of these patent documents. Further, for example, International Publication No. 2003/051092 pamphlet (Japanese Patent Publication No. 2005-513713) discloses a dibenzofluorene compound having an aryl-substituted amino (see Patent Document 4). However, only the structural formula is disclosed in the document, and its specific characteristics are not reported.

International Publication No. 2004/061047 Pamphlet International Publication No. 2004/061048 (Special Publication 2006-512395) International Publication No. 2005/056633 Pamphlet International Publication No. 2003/051092 (Special Publication 2005-513713 Publication)

  However, an organic electroluminescent device having sufficient performance with respect to the device life and the like has not been obtained yet even if the organic material described above is used. Under such circumstances, it has been desired to develop an organic electroluminescent device having higher performance in device lifetime, that is, a compound capable of obtaining the device.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found a benzofluorene compound represented by the following general formula (1) and succeeded in the production thereof. In addition, the present inventors have found that an organic electroluminescence device improved in device lifetime and the like can be obtained by arranging an organic electroluminescence device by arranging a layer containing this benzofluorene compound between a pair of electrodes. Completed. That is, the present invention provides the following benzofluorene compounds.

上記一般式中、
Ｒは、それぞれ独立して、炭素数１〜６のアルキル、炭素数３〜６のシクロアルキル、炭素数１〜４のアルキルで置換されていてもよい炭素数６〜２４のアリール、または炭素数１〜４のアルキルで置換されていてもよい炭素数２〜２４のヘテロアリールであり、
ＡおよびＢのいずれか一方は上記一般式（２）で表される基であり、もう一方は上記一般式（３）で表される基であり、
Ｒ^１は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜６のアルキル、炭素数３〜６のシクロアルキル、炭素数６〜１０のアリール、または炭素数１〜４のアルキルで置換されているシリルであり、
ｎは、それぞれ独立して、０〜５の整数であり、そして、
上記一般式（１）で表される化合物における少なくとも１つの水素が重水素で置換されていてもよい。[1] A benzofluorene compound represented by the following general formula (1).

In the above general formula,
R each independently represents alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 24 carbon atoms which may be substituted with alkyl having 1 to 4 carbon atoms, or carbon number A heteroaryl having 2 to 24 carbon atoms which may be substituted with 1 to 4 alkyls;
One of A and B is a group represented by the general formula (2), and the other is a group represented by the general formula (3).
R ¹ is each independently substituted with a hydrogen atom, a fluorine atom, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, an aryl having 6 to 10 carbon atoms, or an alkyl having 1 to 4 carbon atoms. Has been Cyril,
n is each independently an integer of 0 to 5, and
At least one hydrogen in the compound represented by the general formula (1) may be substituted with deuterium.

上記一般式（１−１）中、
Ｒは、それぞれ独立して、炭素数１〜６のアルキル、炭素数３〜６のシクロアルキル、または炭素数１〜４のアルキルで置換されていてもよい炭素数６〜１２のアリールであり、
Ｒ^１は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜６のアルキル、炭素数３〜６のシクロアルキル、炭素数６〜１０のアリール、または炭素数１〜４のアルキルで置換されているシリルであり、そして、
ｎは、それぞれ独立して、０〜５の整数である。[2] The benzofluorene compound described in the above [1], which is represented by the following general formula (1-1).

In the general formula (1-1),
Each R is independently a C 1-6 alkyl, a C 3-6 cycloalkyl, or a C 6-12 aryl optionally substituted with a C 1-4 alkyl;
R ¹ is each independently substituted with a hydrogen atom, a fluorine atom, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, an aryl having 6 to 10 carbon atoms, or an alkyl having 1 to 4 carbon atoms. Being Cyril, and
n is an integer of 0-5 each independently.

上記一般式（１−２）中、
Ｒは、それぞれ独立して、炭素数１〜６のアルキル、炭素数３〜６のシクロアルキル、または炭素数１〜４のアルキルで置換されていてもよい炭素数６〜１２のアリールであり、
Ｒ^１は、それぞれ独立して、水素原子、フッ素原子、炭素数１〜６のアルキル、炭素数３〜６のシクロアルキル、炭素数６〜１０のアリール、または炭素数１〜４のアルキルで置換されているシリルであり、そして、
ｎは、それぞれ独立して、０〜５の整数である。[3] The benzofluorene compound described in the above [1], which is represented by the following general formula (1-2).

In the general formula (1-2),
Each R is independently a C 1-6 alkyl, a C 3-6 cycloalkyl, or a C 6-12 aryl optionally substituted with a C 1-4 alkyl;
R ¹ is each independently substituted with a hydrogen atom, a fluorine atom, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, an aryl having 6 to 10 carbon atoms, or an alkyl having 1 to 4 carbon atoms. Being Cyril, and
n is an integer of 0-5 each independently.

[4] Each R is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclohexyl, phenyl or naphthyl;
Each R ¹ independently represents a hydrogen atom, a fluorine atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl, triethylsilyl or dimethylmono; t-butylsilyl and
n is each independently an integer of 0 to 2,
The benzofluorene compound described in [2] or [3] above.

[5] Each R is independently methyl, ethyl, isopropyl, s-butyl, t-butyl, or phenyl;
Each R ¹ is independently a hydrogen atom, a fluorine atom, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl or trimethylsilyl, and
n is each independently an integer of 0 to 2,
The benzofluorene compound described in [2] or [3] above.

上記式中、ＴＭＳはトリメチルシリルを表す。[6] The benzofluorene compound according to the above [1], represented by the following formula (1-1-11).

In the above formula, TMS represents trimethylsilyl.

上記式中、ＴＭＳはトリメチルシリルを表す。[7] The benzofluorene compound according to the above [1], represented by the following formula (1-2-11).

In the above formula, TMS represents trimethylsilyl.

[8] The benzofluorene compound according to the above [1], represented by the following formula (1-2-1).

[9] The benzofluorene compound according to the above [1], represented by the following formula (1-1-1).

[10] The benzofluorene compound according to the above [1], represented by the following formula (1-1-46).

[11] A material for a light emitting layer of a light emitting element, the material for a light emitting layer containing the benzofluorene compound according to any one of the above [1] to [10].

[12] An organic electroluminescent element comprising a pair of electrodes composed of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes and containing the light emitting layer material described in [11] above.

[13] Furthermore, it has an electron transport layer and / or an electron injection layer arranged between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer is a quinolinol-based metal complex, The organic electroluminescent device according to [12] above, which contains at least one selected from the group consisting of a pyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative.

[14] The electron transport layer and / or the electron injection layer may further include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth. Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes The organic electroluminescent element as described in [13] above.

[15] A display device comprising the organic electroluminescent element as described in any one of [12] to [14].

[16] An illumination device comprising the organic electroluminescent element according to any one of [12] to [14].

  According to a preferred embodiment of the present invention, for example, a benzofluorene compound having excellent characteristics as a light emitting layer material can be provided. Moreover, the organic electroluminescent element improved about characteristics, such as element lifetime, can be provided.

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

1. Benzofluorene compound represented by the general formula (1) The benzofluorene compound of the present invention will be described in detail. The benzofluorene compound according to the present invention is a benzofluorene compound represented by the general formula (1). The benzofluorene compounds represented by the general formulas (1-1) and (1-2) are one embodiment of the benzofluorene compound represented by the general formula (1), and R in each formula Or R ¹ correspond to each other.

  The “alkyl having 1 to 6 carbon atoms” in R of the general formula (1) may be either a straight chain or branched chain (straight chain alkyl having 1 to 6 carbon atoms or branched chain having 3 to 6 carbon atoms). Alkyl). Preferably, it is a C1-C4 alkyl (C3-C4 branched alkyl).

  Specific examples of “alkyl” include methyl (Me), ethyl (Et), n-propyl, isopropyl (i-Pr), n-butyl, isobutyl, s-butyl, t-butyl (t-Bu), n -Pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like.

  Examples of the “C3-C6 cycloalkyl” in R of the general formula (1) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, and cycloheptyl.

  As "C6-C24 aryl" in R of General formula (1), Preferably it is C6-C16 aryl, More preferably, it is C6-C12 aryl.

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

  The “heteroaryl having 2 to 24 carbon atoms” in R of the general formula (1) is preferably a heteroaryl having 2 to 20 carbon atoms, more preferably a heteroaryl having 2 to 15 carbon atoms, and particularly preferably Is a heteroaryl having 2 to 10 carbon atoms. Examples of the “heteroaryl” include a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituent atom, such as an aromatic heterocyclic group. Can be given.

  Examples of the “heterocyclic group” include pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, indolyl, isoindolyl, 1H-indazolyl, Benzimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothazinyl, phenazinyl, etc. Imidazolyl, pyridyl, carbazolyl and the like are preferable.

  Examples of the `` aromatic heterocyclic group '' include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, Benzofuranyl, isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl , Purinyl, pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, phena Cycloalkenyl, phenoxathiinyl, thianthrenyl, etc. indolizinyl, and the like, thienyl, imidazolyl, pyridyl, such as carbazolyl are preferable.

  “Aryl” or “heteroaryl” in R may be substituted with alkyl having 1 to 4 carbon atoms. In this case, examples of the substituent include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Examples include s-butyl and t-butyl, and methyl is preferred. The number of substituents is, for example, the maximum number of substituents, and is preferably 1 to 3, more preferably 1 to 2, and still more preferably 1. However, it is preferable that there is no “substituent”.

^{R 1} in the general formula (2) or formula (3) are each independently a hydrogen atom, a fluorine atom, an alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, 6 to 10 carbon atoms Selected from the group consisting of aryl and silyl substituted with alkyl having 1 to 4 carbon atoms, among which "alkyl", "cycloalkyl", and "aryl" are the same as those described above It is done.

As “silyl substituted with alkyl having 1 to 4 carbon atoms” in R ¹ of general formula (2) or general formula (3), three hydrogens in the silyl group are each independently methyl, ethyl, Examples thereof include those substituted with n-propyl, isopropyl, n-butyl, s-butyl, t-butyl and the like.

  Specific “substituted silyls” include trimethylsilyl (TMS), triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tris-butylsilyl, tri-t-butylsilyl, ethyldimethylsilyl, propyldimethylsilyl, isopropyldimethylsilyl. Butyldimethylsilyl, s-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, s-butyldiethylsilyl, t-butyldiethylsilyl, methyldipropylsilyl, Ethyldipropylsilyl, butyldipropylsilyl, s-butyldipropylsilyl, t-butyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, Le diisopropylsilyl, s- butyl diisopropylsilyl, etc. t- butyl diisopropyl silyl and the like.

  N in the general formula (2) or the general formula (3) is each independently an integer of 0 to 5, preferably n is an integer of 0 to 3, more preferably n is an integer of 0 to 2, and further preferable n is 0.

Further, in the compound represented by the general formula (1), a hydrogen atom in the benzofluorene ring, an R group substituted on the benzofluorene ring, a group represented by the general formula (2), and the general formula (3) All or a part of the hydrogen atoms in the groups represented by the substituent R ¹ to these groups may be deuterium.

  Specific examples of the compound represented by the general formula (1) include, for example, the following formulas (1-1-1) to (1-1-46) and the following formulas (1-2-1) to ( 1-2-46).

2. Production method of benzofluorene compound As represented by the general formula (1), a compound in which an N, N-diphenylamino group is bonded to one side of a benzofluorene skeleton and an N-naphthyl-N-phenylamino group is bonded to the other side It can be produced using existing reactions such as the Buchwald-Hartwig reaction or the Ullmann reaction. However, the compound represented by the general formula (1) is an asymmetric compound, and in the production, a selective reaction is used by utilizing a difference in activity of reactive substituents, or a purification separation technique is used. It is preferable.

  The Buchwald-Hartwig reaction is a method of coupling an aromatic halide with a primary aromatic amine or a secondary aromatic amine using a palladium catalyst in the presence of a base. Specific examples of the reaction route for obtaining the compound represented by the general formula (1) by this method are as follows (Schemes 1 and 2).

The reaction shown in the first stage of Scheme 1 is Suzuki coupling, and the X ¹ group and the X ² group are different so that the Y group and the X ¹ group in the two compounds to be reacted react selectively. Based on reaction activity. Considering the availability of raw materials, for example, a compound in which the X ¹ group is triflate and the X ² group is chlorine is preferable. Further, it is also possible to react interchanging the group X ¹ and Y groups to each other in the two compounds to be reacted. In this case, the reaction activity of the Y group and X ² group substituted for benzoate is set so that Y group> X ² group. Further, in this first stage reaction, Negishi coupling can be used instead of Suzuki coupling. In this case, a zinc chloride complex is used instead of boronic acid or boronic acid ester as the compound having Y group. . Also in the case of this Negishi coupling, the reaction can be carried out even if the X ¹ group and the Y group are interchanged with each other (that is, using a zinc chloride complex of benzoate) as described above. Furthermore, in Scheme 1, in order to form a five-membered ring after the coupling reaction, a raw material in which —COOR ² is previously substituted next to the carbon to be coupled to the benzene ring is used, but the 2-position of the naphthalene ring is used. A raw material in which -COOR ² is substituted (next to the carbon to be coupled) can also be used. For the method of synthesizing the aromatic halide described in Scheme 1, for example, International Publication No. 2005/056633 pamphlet is helpful.

The monohalogen of benzofluorene is obtained by the reaction up to the third stage of Scheme 1. Subsequently, a dihalogen of benzofluorene is obtained by performing the halogenation reaction in the fourth stage, and can be used in Scheme 2 described later. As described above, since the reaction activity of the X ² group (for example, chlorine) is low, the halogenating agent used in the fourth stage is the reason why a higher reaction activity group is introduced into the X ³ group. For example, a brominating agent or an iodinating agent is preferable, and an iodinating agent is more preferable.

Scheme 2, the compound represented by the general formula (1) benzo fluorene skeleton, firstly, N to X ³ group side, N- diphenylamino group reacted, then, N- naphthyl -N to X ² group side -A method for forming a phenylamino group. In this case, the compound represented by the general formula (1-1) is synthesized. However, by replacing the reaction order of the N, N-diphenylamino group and the N-naphthyl-N-phenylamino group, the general formula (1) -2) can also be synthesized.

R, R ¹ and n in each scheme correspond to those used in the general formula (1).

Specific examples of the palladium catalyst used in the above reaction are tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , Palladium (II) acetate: Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (dba ₃ ) CHCl ₃ , bis (dibenzylideneacetone) palladium (0): Pd (dba) ₂ , PdCl ₂ {P (t-Bu) _2- (p-NMe ₂ -Ph)} ₂ , dichlorobis (tri-o -Tolylphosphine) palladium (II) and the like.

  In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds in some cases. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (di-t-butylphosphino) ferrocene, 1- (methoxymethyl). 2- (di-t-butylphosphino) ferrocene, 1,1′-bis (di-t-butylphosphino) ferrocene, 2,2′-bis (di-t-butylphosphino) -1,1′-binaphthyl 2-methoxy-2 ′-(di-t-butylphosphino) -1,1′-binaphthyl, 1,1′-bis (diphenylphosphino) ferrocene, bis (diphenylphosphino) binaphthyl, 4-dimethylaminophenyl Examples thereof include di-t-butylphosphine and phenyldi-t-butylphosphine.

  Specific examples of the base used in this reaction are sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, phosphoric acid. Tripotassium, potassium fluoride, etc.

  Specific examples of the solvent used in this reaction are benzene, 1,2,4-trimethylbenzene, toluene, xylene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, t-butyl methyl ether, 1,4- Dioxane, methanol, ethanol, isopropyl alcohol and the like. These solvents can be appropriately selected according to the structures of the aromatic halide, triflate, aromatic boronic acid ester and aromatic boronic acid to be reacted. A solvent may be used independently and may be used as a mixed solvent.

  The Ullmann reaction is a method of coupling an aromatic halide and a primary aromatic amine or a secondary aromatic amine using a copper catalyst in the presence of a base. Specific examples of the copper catalyst used in the Ullmann reaction include copper powder, copper chloride, copper bromide or copper iodide. Moreover, the specific example of the base used by this reaction can be selected from the same thing as Buchwald-Hartwig reaction. Furthermore, specific examples of the solvent used in the Ullmann reaction include nitrobenzene, dichlorobenzene, N, N-dimethylformamide and the like.

Moreover, the compound represented by General formula (1) can be manufactured also using the following reaction (Scheme 3). Note that the reaction shown in the first stage of Scheme 3 is Suzuki coupling, and the reaction can be performed by alternately exchanging the X group and the Y group in the two compounds to be reacted. Further, in this first stage reaction, Negishi coupling can be used instead of Suzuki coupling. In this case, a zinc chloride complex is used instead of boronic acid or boronic acid ester as the compound having Y group. . In the case of this Negishi coupling, the reaction can be carried out even if the X group and the Y group are alternately replaced in the same manner as described above. In addition, R, R ¹ and n in each scheme correspond to those used in the general formula (1), respectively.

  As in Scheme 2, a synthesis example of the compound represented by the general formula (1-1) is shown as an example, but the compound represented by the general formula (1-2) can be obtained by appropriately changing the starting triarylamine derivative. Can also be synthesized.

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

3. Organic Electroluminescent Device The benzofluorene compound according to the present invention can be used as a material for an organic electroluminescent device, for example.
The organic electroluminescent element according to this embodiment will be described in detail based on the drawings. FIG. 1 is a schematic cross-sectional view showing an organic electroluminescent element according to this embodiment.

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

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

  Not all of the above layers are necessary, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection are included. The layer 107 is an arbitrarily provided layer. Each of the layers may be composed of a single layer or a plurality of layers.

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

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

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

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

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

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

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

  As a material for forming the hole injection layer 103 and the hole transport layer 104, in a photoconductive material, a compound conventionally used as a charge transport material for holes, a p-type semiconductor, and a hole injection of an organic electroluminescent element are used. Any known material used for the layer and the hole transport layer can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amino in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4 , 4'-diaminobiphenyl, N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl (hereinafter abbreviated as NPD), N, N'-diphenyl-N, N'- Di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl -4,4′-diphenyl-1,1′-diamine, triphenylamine derivatives such as 4,4 ′, 4 ″ -tris (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, etc.) , Stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. Polycarbonate, styrene derivatives, polyvinyl carbazole, polysilane, etc. having monomers in the side chain are preferred, but a compound that forms a thin film necessary for the production of a light-emitting element, can inject holes from the anode, and can further transport holes If it is especially limited Not.

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

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

  The light emitting layer may be either a single layer or a plurality of layers, each formed of a light emitting material (host material, dopant material), which may be a mixture of a host material and a dopant material or a host material alone. Or either. That is, in each layer of the light emitting layer, only the host material or the dopant material may emit light, or both the host material and the dopant material may emit light. Each of the host material and the dopant material may be one kind or a plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. The amount of dopant used varies depending on the dopant and may be determined according to the characteristics of the dopant. The standard of the amount of the dopant used is preferably 0.001 to 50% by weight, more preferably 0.1 to 10% by weight, and further preferably 1 to 5% by weight of the entire light emitting material. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

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

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

  The amount of the host material used is preferably 50 to 99.999% by weight of the entire light emitting material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight.

  Moreover, as a dopant material, the benzofluorene compound of the said General formula (1) can be used, Especially the compound represented by the said General formula (1-1) or the said General formula (1-2), Furthermore, the said It is preferable to use a compound represented by Formula (1-1-1) to Formula (1-1-40) or the above Formula (1-2-1) to Formula (1-2-40). The amount of the benzofluorene compound represented by the general formula (1) used as a dopant material is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, based on the entire luminescent material. More preferably, it is 0.1 to 10% by weight. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited.

  Other dopant materials can be used at the same time. The other dopant material is not particularly limited, and a known compound can be used, and can be selected from various materials according to a desired emission color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene and rubrene, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazole derivatives, Bisstyryl derivatives such as oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives and distyrylbenzene derivatives Kaihei 1-245087), bisstyrylarylene derivatives (Japanese Patent Laid-Open No. 2-247278) Isobenzofuran derivatives such as diazaindacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, Dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3-benzoimidazolylcoumarin derivatives , Coumarin derivatives such as 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, cyanine derivatives , Oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2, 5-thiadiazolopyrene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, and deazaflavin derivatives.

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

  Examples of green to yellow dopant materials include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, and naphthacene derivatives such as rubrene, and the above blue The compound which introduce | transduced the substituent which enables long wavelength, such as aryl, heteroaryl, aryl vinyl, amino, and cyano to the compound illustrated as a blue-green dopant material is also mentioned as a suitable example.

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

  As the dopant material suitable for the light emitting layer material of the present invention, among the above-mentioned dopant materials, the benzofluorene compound represented by the general formula (1) is most suitable. , Borane derivatives, amine-containing styryl derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, iridium complexes or platinum complexes are preferred.

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

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

  Examples of the amine-containing styryl derivative include N, N, N ′, N′-tetra (4-biphenylyl) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (1-naphthyl). -4,4'-diaminostilbene, N, N, N ', N'-tetra (2-naphthyl) -4,4'-diaminostilbene, N, N'-di (2-naphthyl) -N, N' -Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis ( Diphenylamino) styryl] -biphenyl, 1,4-bis [4′-bis (diphenylamino) styryl] -benzene, 2,7-bis [4′-bis (diphenylamino) styryl] -9,9-dimethylfluorene , 4, 4 ' Examples thereof include bis (9-ethyl-3-carbazovinylene) -biphenyl, 4,4′-bis (9-phenyl-3-carbazovinylene) -biphenyl, etc. JP-A 2003-347056 and JP-A 2001- An amine-containing styryl derivative described in Japanese Patent No. 307884 may be used.

Examples of the aromatic amine derivative include N, N, N, N-tetraphenylanthracene-9,10-diamine, 9,10-bis (4-diphenylamino-phenyl) anthracene, and 9,10-bis (4- Di (1-naphthylamino) phenyl) anthracene, 9,10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p-tolylamino-9- (4-di-p-tolylamino-1) -Naphthyl) anthracene, 10-diphenylamino-9- (4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino-9- (6-diphenylamino-2-naphthyl) anthracene, [4- (4-diphenyl) Amino-phenyl) naphthalen-1-yl] -diphenylamine, [6- (4-diphenylamino-phenyl) Naphthalen-2-yl] -diphenylamine, 4,4′-bis [4-diphenylaminonaphthalen-1-yl] biphenyl, 4,4′-bis [6-diphenylaminonaphthalen-2-yl] biphenyl, 4,4 "-Bis [4-diphenylaminonaphthalen-1-yl] -p-terphenyl, 4,4" -bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl, and the like.
Moreover, you may use the aromatic amine derivative described in Unexamined-Japanese-Patent No. 2006-156888.

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

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

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

また、特開2006-089398号公報、特開2006-080419号公報、特開2005-298483号公報、特開2005-097263号公報、および特開2004-111379号公報などに記載されたイリジウム錯体を用いてもよい。Examples of the iridium complex include Ir (ppy) _{3 described} below.

Further, the iridium complexes described in JP-A-2006-089398, JP-A-2006-080419, JP-A-2005-298483, JP-A-2005-097263, JP-A-2004-111379, etc. It may be used.

また、特開2006-190718号公報、特開2006-128634号公報、特開2006-093542号公報、特開2004-335122号公報、および特開2004-331508号公報などに記載された白金錯体を用いてもよい。Examples of the platinum complex include the following PtOEP.

Further, the platinum complexes described in JP-A-2006-190718, JP-A-2006-128634, JP-A-2006-093542, JP-A-2004-335122, JP-A-2004-331508, etc. It may be used.

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

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

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

  Materials used for the electron transport layer and the electron injection layer include compounds conventionally used as electron transport compounds in photoconductive materials, and known compounds used for the electron injection layer and the electron transport layer of organic electroluminescent elements. Any of these can be selected and used.

  Specifically, pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone derivatives, perylene derivatives, thiophene derivatives, thiadiazole derivatives, quinoxaline derivatives, quinoxaline Derivative polymers, benzazole compounds, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, imidazopyridine derivatives, borane derivatives, benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, aldazine derivatives, carbazole derivatives, indole derivatives, Examples thereof include phosphorus oxide derivatives and bisstyryl derivatives. In addition, oxadiazole derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), triazole derivatives (N-naphthyl-2,5-diphenyl-1,3, etc.) 4-triazole etc.), benzoquinoline derivatives (2,2′-bis (benzo [h] quinolin-2-yl) -9,9′-spirobifluorene etc.), benzimidazole derivatives (tris (N-phenylbenzimidazole) -2-yl) benzene), bipyridine derivatives, terpyridine derivatives (1,3-bis (4 ′-(2,2 ′: 6′2 ″ -terpyridinyl)) benzene, etc.), naphthyridine derivatives (bis (1-naphthyl) ) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide, etc.) These materials are But it used but may be used in admixture with different materials.

  In addition, metal complexes having electron-accepting nitrogen can also be used, such as hydroxyazole complexes such as quinolinol-based metal complexes and hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. can give. These materials can be used alone or in combination with different materials.

  Among the materials described above, quinolinol metal complexes, pyridine derivatives, phenanthroline derivatives, borane derivatives or benzimidazole derivatives are preferable.

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

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

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

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

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

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

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

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

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

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

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

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

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, X is an optionally substituted arylene, and Y is a substituted And optionally substituted aryl having 16 or less carbon atoms, substituted boryl, or optionally substituted carbazole, and n is each independently an integer of 0 to 3.

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

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl, or an optionally substituted aryl, and R ²¹ and R ²² are each independently hydrogen, alkyl, substituted. At least one of optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring, or cyano, X ¹ is an optionally substituted arylene having 20 or less carbon atoms, and n is each Each independently represents an integer of 0 to 3, and each m independently represents an integer of 0 to 4;

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

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

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

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, X ¹ is an optionally substituted arylene having 20 or less carbon atoms, And n is an integer of 0-3 each independently.

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

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

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

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocycle, or cyano, R ^{13 to} R ¹⁶ are each independently an optionally substituted alkyl or an optionally substituted aryl, X ¹ is an optionally substituted arylene having 10 or less carbon atoms, Y ¹ is an optionally substituted aryl having 14 or less carbon atoms, and n is each independently an integer of 0 to 3.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the display device include a panel display such as a color flat panel display, and a flexible display such as a flexible color organic electroluminescence (EL) display (for example, JP-A-10-335066 and JP-A-2003-321546). Gazette, Japanese Patent Application Laid-Open No. 2004-281086, etc.). Examples of the display method of the display include a matrix and / or segment method. Note that the matrix display and the segment display may coexist in the same panel.

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

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

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

<Synthesis example of benzofluorene compound>
Hereinafter, it is represented by Formula (1-1-11), Formula (1-2-11), Formula (1-1-1), Formula (1-2-1), and Formula (1-1-46). A synthesis example of the compound will be described.

[Synthesis Example 1] Synthesis of Compound (1-1-11)

<Synthesis of methyl 5-chloro-2- (naphthalen-1-yl) benzoate>
Under a nitrogen atmosphere, 1-naphthaleneboronic acid (38.0 g), methyl 2-bromo-5-chlorobenzoate (50.0 g), Pd (PPh ₃ ) ₄ (2.3 g), potassium phosphate (85.0 g) ), Toluene (500 ml), 2-propanol (150 ml) and water (50 ml) were stirred at reflux temperature for 2 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water was added for liquid separation, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography (developing solution: toluene / heptane mixed solvent). At this time, referring to the method described in “Chemical Doujin Shuppan Co., Ltd.,” page 94, “Tobiki of Organic Chemistry Experiment (1)-Substance Handling Method and Separation Purification Method”, gradually increase the ratio of toluene in the developing solution. Increased to elute the desired product. The eluate was distilled off under reduced pressure to obtain methyl 5-chloro-2- (naphthalen-1-yl) benzoate (58.3 g).

<Synthesis of 2- (5-chloro-2- (naphthalen-1-yl) phenylpropan-2-ol>
Under a nitrogen atmosphere, a solution of methyl 5-chloro-2- (naphthalen-1-yl) benzoate (58.0 g) in THF (250 ml) was cooled in a water bath, and methyl magnesium bromide THF solution (1 .1M, 300 ml) was added dropwise. The water bath was removed after completion | finish of dripping, and it stirred at 30 degreeC for 3 hours. Then, it cooled in the ice bath, ammonium chloride aqueous solution was added, reaction was stopped, and about half amount of THF was depressurizingly distilled. Ethyl acetate was added to the solution and the phases were separated, and the solvent was evaporated under reduced pressure. The obtained solid was purified by activated alumina column chromatography (developing solution: toluene / heptane mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of toluene in the developing solution. Subsequently, after evaporating the eluate under reduced pressure, the obtained solid was washed with heptane to obtain 2- (5-chloro-2- (naphthalen-1-yl) phenylpropan-2-ol (43.0 g). It was.

<Synthesis of 9-chloro-7,7-dimethyl-7H-benzo [c] fluorene>
Under a nitrogen atmosphere, a flask containing boron tribromide diethyl ether complex (29.0 g) and chloroform (400 ml) was cooled in an ice bath, and 2- (5-chloro-2- (naphthalen-1-yl) was added thereto. A chloroform solution of phenylpropan-2-ol (43.0 g) was added dropwise, after which the ice bath was removed, the mixture was stirred at room temperature for 1 hour, water was added to stop the reaction, and then sodium bicarbonate was added. Neutralization, liquid separation, and removal of the solvent under reduced pressure gave 9-chloro-7,7-dimethyl-7H-benzo [c] fluorene (41.3 g).

<Synthesis of 9-chloro-5-iodo-7,7-dimethyl-7H-benzo [c] fluorene>
Of 9-chloro-7,7-dimethyl-7H-benzo [c] fluorene (41.3 g), iodine (3.9 g), orthoperiodic acid (2.6 g), acetic acid (200 ml) and sulfuric acid (4 ml) The flask was stirred at 100 ° C. for 4 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, an aqueous sodium hydrogen sulfite solution was added to stop the reaction, and ethyl acetate was further added to separate the layers. The solvent was distilled off under reduced pressure, and the obtained oily substance was purified with a silica gel short column (developing solution: toluene). Further purification was performed by silica gel column chromatography (developing solution: heptane) to obtain 9-chloro-5-iodo-7,7-dimethyl-7H-benzo [c] fluorene (8.1 g).

<Synthesis of 9-chloro-7,7-dimethyl-N-phenyl-N- (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluoren-5-amine>
N-phenyl-4- (trimethylsilyl) aniline (0.67 g), 9-chloro-5-iodo-7,7-dimethyl-7H-benzo [c] fluorene (4.0 g), dichlorobis (tri-o-tolyl) A flask containing phosphine) palladium (II) (0.4 g), sodium-t-butoxide (0.50 g) and 1,2,4-trimethylbenzene (30 ml) was stirred at 140 ° C. for 6 hours under a nitrogen atmosphere. . After cooling the reaction solution to room temperature, water and ethyl acetate were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography (developing solution: toluene / heptane / ethyl acetate / triethylamine = 5/95/1/1 (volume ratio)). After the solvent was distilled off under reduced pressure, the obtained solid was recrystallized from heptane to give 9-chloro-7,7-dimethyl-N-phenyl-N- (4- (trimethylsilyl) phenyl) -7H-benzo [c Fluoren-5-amine (3.2 g) was obtained.

<Synthesis of Compound (1-1-11)>
N-phenylnaphthalen-1-amine (0.81 g), 9-chloro-7,7-dimethyl-N-phenyl-N- (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluoren-5-amine (1.6 g), Pd (dba) ₂ (0.02 g), 4- (di-t-butylphosphino) -N, N-dimethylaniline (0.03 g), sodium-t-butoxide (0.5 g) ) And 1,2,4-trimethylbenzene (15 ml) were stirred at 150 ° C. for 2 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and ethyl acetate were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography (developing solution: toluene / heptane / ethyl acetate / triethylamine = 5/95/3/1 (volume ratio)). After the solvent was distilled off under reduced pressure, a precipitate formed by adding heptane to the obtained oily substance was collected, and further washed with methanol to obtain a compound represented by the formula (1-1-11), 7, 7-dimethyl -N ⁹ - ^{(naphthalen-1-yl)} -N 5, ^{N 9} - diphenyl ^-N 5 - (4-(trimethylsilyl) phenyl)-7H-benzo [c] fluorene-5,9-diamine (1 .3 g) was obtained.

The structure of the compound represented by the formula (1-1-11) was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.64 (d, 1H), 8.09 (d, 1H), 8.03 (d, 1H), 7.97 (d, 1H), 7.90 (D, 1H), 7.79 (d, 1H), 6.90-7.55 (m, 23H), 1.36 (s, 6H), 0.22 (s, 9H).

[Synthesis Example 2] Synthesis of Compound (1-2-11)

<Synthesis of 9-chloro-7,7-dimethyl-N- (naphthalen-1-yl) -N-phenyl-7H-benzo [c] fluoren-5-amine>
N-phenylnaphthalen-1-amine (1.1 g), 9-chloro-5-iodo-7,7-dimethyl-7H-benzo [c] fluorene (2.0 g), dichlorobis (tri-o-tolylphosphine) A flask containing palladium (II) (0.2 g), sodium-t-butoxide (0.7 g) and 1,2,4-trimethylbenzene (20 ml) was stirred at 140 ° C. for 12 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and ethyl acetate were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography (developing solution: toluene / heptane / ethyl acetate = 9/90/1 (volume ratio)). After the solvent was distilled off under reduced pressure, the obtained solid was washed with heptane, and 9-chloro-7,7-dimethyl-N- (naphthalen-1-yl) -N-phenyl-7H-benzo [c] fluorene. -5-amine (1.0 g) was obtained.

<Synthesis of Compound (1-2-11)>
N-phenyl-4- (trimethylsilyl) aniline (0.53 g), 9-chloro-7,7-dimethyl-N- (naphthalen-1-yl) -N-phenyl-7H-benzo [c] fluorene-5 Amine (1.0 g), Pd (dba) ₂ (0.02 g), 4- (di-t-butylphosphino) -N, N-dimethylaniline (0.03 g), sodium-t-butoxide (0. The flask containing 5 g) and 1,2,4-trimethylbenzene (15 ml) was stirred at 150 ° C. for 4 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and ethyl acetate were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel chromatography (developing solution: toluene / heptane / ethyl acetate / triethylamine = 5/95/2/1 (volume ratio)). After the solvent was distilled off under reduced pressure, the obtained oily substance was dissolved in ethanol and reprecipitated by adding water, and the compound represented by the formula (1-2-11), 7,7-dimethyl-N ⁵ - (4-(trimethylsilyl) phenyl)-7H-benzo [c] fluorene-5,9-diamine (0.9 g) - ^{(naphthalen-1-yl)} -N 5, ^{N 9} - diphenyl ^-N 9 .

The structure of the compound represented by Formula (1-2-11) was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.67 (d, 1H), 8.15 (t, 2H), 8.08 (d, 1H), 7.88 (d, 1H), 7.68 (D, 1H), 7.55 (t, 1H), 7.47 (t, 1H), 7.00-7.40 (m, 19H), 6.87 (m, 1H), 6.74 ( m, 1H), 1.32 (s, 6H), 0.26 (s, 9H).

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

<Synthesis of N, N-diphenyl-4- (trimethylsilyl) naphthalen-1-amine>
(4-bromonaphthalen-1-yl) trimethylsilane (167.5 g), diphenylamine (101.5 g), palladium acetate (0.03 g) synthesized by the synthesis method described in Organometallics 2009, 28, 3004-3011, A flask containing tri-tert-butylphosphine (0.12 g), sodium-t-butoxide (69.2 g) and o-xylene (1800 ml) was stirred at reflux temperature for 8 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, the salt content was removed by suction filtration using a Kiriyama funnel with silica gel. The filtrate was distilled off under reduced pressure and the resulting solid was recrystallized from a heptane / toluene mixed solvent to obtain N, N-diphenyl-4- (trimethylsilyl) naphthalen-1-amine (180.0 g).

<Synthesis of 4-bromo-N, N-diphenylnaphthalen-1-amine>
Under a nitrogen atmosphere, a flask containing N, N-diphenyl-4- (trimethylsilyl) naphthalen-1-amine (176.4 g) and chloroform (2700 ml) was stirred with cooling in an ice bath, and N-bromosuccinate was added thereto. Acid imide (101.5 g) was added. Then, it heated up to room temperature, and also stirred for 1 hour, and reaction was stopped. The reaction solution was filtered by suction filtration, and the solvent of the filtrate was distilled off under reduced pressure. The obtained solid was recrystallized from a heptane / toluene mixed solvent to obtain 4-bromo-N, N-diphenylnaphthalen-1-amine (128.0 g).

<Synthesis of N, N-diphenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalen-1-amine>
4-bromo-N, N-diphenylnaphthalen-1-amine (47.0 g), bispinacolato diborane (48.0 g), Pd (dppf) Cl ₂ (3.0 g), potassium acetate (37.0 g) and A flask containing cyclopentyl methyl ether (300 ml) was stirred at reflux temperature for 4 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and ethyl acetate were added and the layers were separated. The solvent was distilled off under reduced pressure, the obtained solid was dissolved in toluene, and a silica gel short column was performed. The solvent was distilled off again under reduced pressure, and the resulting solid was washed with heptane to give N, N-diphenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl. ) Naphthalen-1-amine (50.0 g) was obtained.

<Synthesis of methyl 5-chloro-2- (4- (diphenylamino) naphthalen-1-yl) benzoate>
N, N-diphenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalen-1-amine (50.0 g), methyl 2-bromo-5 Flask containing chlorobenzoate (26.4 g), Pd (PPh ₃ ) ₄ (1.3 g), potassium phosphate (47.0 g), xylene (370 ml), 2-propanol (100 ml) and water (30 ml) Was stirred at reflux temperature for 2 hours under a nitrogen atmosphere. After cooling the reaction solution to room temperature, water and ethyl acetate were added and the layers were separated. The solvent was distilled off under reduced pressure, and the resulting oily substance was purified by silica gel column chromatography (developing solution: toluene / heptane mixed solvent) to obtain methyl 5-chloro-2- (4- (diphenylamino) naphthalen-1-yl. ) Benzoate (49.0 g) was obtained. At this time, the target product was eluted by gradually increasing the ratio of toluene in the developing solution.

<Synthesis of 2- (5-chloro-2- (4- (diphenylamino) naphthalen-1-yl) phenyl) propan-2-ol>
Under a nitrogen atmosphere, a solution of methyl 5-chloro-2- (4- (diphenylamino) naphthalen-1-yl) benzoate (49.0 g) dissolved in THF (250 ml) was cooled in a water bath, Magnesium bromide THF solution (1.0 M, 295 ml) was added dropwise. The water bath was removed after completion | finish of dripping, and it stirred at 30 degreeC for 4 hours. Then, it cooled in the ice bath, ammonium chloride aqueous solution was added, reaction was stopped, and about half amount of THF was depressurizingly distilled. Ethyl acetate was added to the solution and the phases were separated, and the solvent was evaporated under reduced pressure. The obtained solid was purified by silica gel column chromatography (developing solution: toluene / heptane mixed solvent) to give 2- (5-chloro-2- (4- (diphenylamino) naphthalen-1-yl) phenyl) propane-2. -All (38.0 g) was obtained. At this time, the target product was eluted by gradually increasing the ratio of toluene in the developing solution.

<Synthesis of 9-chloro-7,7-dimethyl-N, N-diphenyl-7H-benzo [c] fluoren-5-amine>
Under a nitrogen atmosphere, a flask containing boron tribromide diethyl ether complex (16.3 g) and chloroform (200 ml) was cooled in an ice bath, and 2- (5-chloro-2- (4- (diphenylamino)) was added thereto. A chloroform solution of naphthalen-1-yl) phenyl) propan-2-ol (38.0 g) was added dropwise. After completion of the dropping, the ice bath was removed and the mixture was stirred at room temperature for 1 hour, and then water was added to stop the reaction. Subsequently, the reaction mixture was neutralized by adding sodium hydrogen carbonate, liquid separation was performed, and the solvent was distilled off under reduced pressure. The obtained solid was washed with heptane to obtain 9-chloro-7,7-dimethyl-N, N-diphenyl-7H-benzo [c] fluoren-5-amine (31.5 g).

<Synthesis of Compound (1-1-1)>
9-chloro-7,7-dimethyl-N, N-diphenyl-7H-benzo [c] fluoren-5-amine (10.0 g), N-phenylnaphthalen-1-amine (5.9 g), Pd (dba ) ₂ (0.15 g), 4- (di-t-butylphosphino) -N, N-dimethylaniline (0.2 g), sodium-t-butoxide (3.2 g) and xylene (100 ml) The flask was stirred at reflux temperature for 2 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, water, ethyl acetate and chlorobenzene were added to separate the layers. The solvent was distilled off under reduced pressure, and the obtained solid was dissolved in chlorobenzene heated and subjected to a silica gel short column. The solvent was distilled off under reduced pressure, and resulting solid was recrystallized from chlorobenzene, compounds represented by formula (1-1-1), 7,7-dimethyl -N ⁹ - (naphthalen-1-yl) -N ^{5, N 5, N 9} - give triphenyl -7H- benzo [c] fluorene 5,9-diamine (12.1 g).

The structure of the compound represented by the formula (1-1-1) was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.62 (m, 1H), 8.00-8.11 (m, 2H), 7.96 (d, 1H), 7.89 (d, 1H) 7.78 (d, 1H), 7.30-7.55 (m, 8H), 6.85-7.25 (m, 16H), 1.35 (s, 6H).

[Synthesis Example 4] Synthesis of Compound (1-2-1)

<Synthesis of Compound (1-2-1)>
7,7-dimethyl -N ⁵ - ^{(naphthalen-1-yl)} -N 5, ^{N 9} - diphenyl ^-N 9 - (4- (trimethylsilyl) phenyl)-7H-benzo [c] fluorene-5,9-diamine A flask containing (0.2 g) and toluene (5 ml) was stirred at room temperature, and one drop of trifluoromethanesulfonic acid was added dropwise thereto. After stirring for about 1 minute, the mixture was neutralized by adding triethylamine. The solvent in the reaction solution was distilled off under reduced pressure, and the residue was purified by silica gel chromatography (developing solution: toluene / heptane / ethyl acetate = 5/95/1 (volume ratio)), and represented by the formula (1-2-1). The compound, 7,7-dimethyl-N ^5- (naphthalen-1-yl) -N ⁵ , N ⁹ , N ⁹ -triphenyl-7H-benzo [c] fluorene 5,9-diamine (0.1 g) is obtained. It was.

The structure of the compound represented by Formula (1-2-1) was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.67 (d, 1H), 8.15 (m, 2H), 8.08 (d, 1H), 7.88 (d, 1H), 7.67 (D, 1H), 7.55 (t, 1H), 7.47 (t, 1H), 7.00-7.38 (m, 20H), 6.86 (m, 1H), 6.74 ( m, 1H), 1.32 (s, 6H).

[Synthesis Example 5] Synthesis of Compound (1-1-46)

<Synthesis of 5-bromo-7,7-dimethyl-7H-benzo [c] fluorene>
Under a nitrogen atmosphere, a flask containing 7,7-dimethyl-7H-benzo [c] fluorene (10.0 g), N-bromosuccinimide (7.3 g) and acetic acid (200 ml) was stirred at 70 ° C. for 1 hour. . After the reaction solution was cooled to room temperature, an aqueous sodium hydrogen sulfite solution and then ethyl acetate were added for liquid separation. The solvent of the organic layer was distilled off under reduced pressure, and the obtained solid was washed with methanol and then recrystallized from a mixed solvent of heptane and then ethyl acetate / ethanol to give 5-bromo-7,7-dimethyl-7H-benzo [ c] Fluorene (11.0 g) was obtained.

<Synthesis of 5-bromo-9-iodo-7,7-dimethyl-7H-benzo [c] fluorene>
Contains 5-bromo-7,7-dimethyl-7H-benzo [c] fluorene (11.0 g), iodine (3.4 g), iodic acid (3.0 g), acetic acid (200 ml) and sulfuric acid (4 ml). The flask was stirred at 120 ° C. for 2 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, an aqueous sodium hydrogen sulfite solution was added to stop the reaction, and then an amount of sodium carbonate capable of neutralizing the sulfuric acid used was added. Further, toluene and water were added for liquid separation, and the solvent of the organic layer was distilled off under reduced pressure, followed by purification by silica gel column chromatography (developing solution: heptane). The solvent was distilled off under reduced pressure, and the resulting oil was reprecipitated by adding heptane to obtain 5-bromo-9-iodo-7,7-dimethyl-7H-benzo [c] fluorene (10.0 g). It was.

<Synthesis of 5-bromo-7,7-dimethyl-N- (naphthalen-1-yl) -N- (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluoren-9-amine>
Under a nitrogen atmosphere, 5-bromo-9-iodo-7,7-dimethyl-7H-benzo [c] fluorene (5.0 g), N- (4- (trimethylsilyl) phenyl) naphthalen-1-amine (3.2 g) ), (PdCl ₂ (o-toly ₃ ) ₂ ) (0.3 g), sodium t-butoxide (1.6 g) and 1,2,4-trimethylbenzene (50 ml) at 90 ° C. Stir for 6 hours. After cooling the reaction solution to room temperature, water and ethyl acetate were added to separate the layers. After the solvent of the organic layer was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (developing solution: toluene / heptane / triethylamine = 5/94/1 (volume ratio)), and 5-bromo-7,7-dimethyl-N. -(Naphthalen-1-yl) -N- (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluoren-9-amine (6.0 g) was obtained.

<7,7-dimethyl -N ⁹ - (naphthalen-1-yl) -N ⁵ - phenyl ^-N 9 - (4- (trimethylsilyl) phenyl)-7H-benzo [c] fluorene-5,9-diamine >
Under a nitrogen atmosphere, 5-bromo-7,7-dimethyl-N- (naphthalen-1-yl) -N- (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluoren-9-amine (6.0 g) ), Aniline (0.8 g), Pd (dba) ₂ (0.04 g), 4- (di-t-butylphosphino) -N, N-dimethylaniline (0.04 g), sodium-t-butoxide ( A flask containing 1.0 g) and xylene (50 ml) was stirred at 80 ° C. for 1 hour. After cooling the reaction solution to room temperature, water and ethyl acetate were added to separate the layers. The solvent of the organic layer was evaporated under reduced pressure, silica gel column chromatography and purified by (eluent toluene / heptane / triethylamine solvent mixture), 7,7-dimethyl -N ⁹ - (naphthalen-1-yl) -N ⁵ - (4-(trimethylsilyl) phenyl)-7H-benzo [c] fluorene-5,9-diamine (4.3 g) - phenyl ^-N 9. At this time, the target product was eluted by gradually increasing the ratio of toluene in the developing solution.

<Synthesis of Compound (1-1-46)>
7,7-dimethyl -N ⁹ - (naphthalen-1-yl) -N ⁵ - phenyl ^-N 9 - (4-(trimethylsilyl) phenyl)-7H-benzo [c] fluorene-5,9-diamine (4. 3 g), (4-bromophenyl) trimethylsilane (1.7 g), Pd (dba) ₂ (0.04 g), 4- (di-t-butylphosphino) -N, N-dimethylaniline (0.03 g) ), Sodium-t-butoxide (0.9 g) and xylene (40 ml) were stirred at 80 ° C. for 1 hour under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. After the solvent of the organic layer was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (developing solution: toluene / heptane / triethylamine = 5/94/1 (volume ratio)), and further activated carbon column chromatography (developing solution: toluene / Heptane / triethylamine = 20/80/1 (volume ratio)). The solvent was distilled off under reduced pressure, the resulting oily substance was precipitated by addition of ethanol solid collected, compounds of formula (1-1-46), 7,7-dimethyl -N ⁹ - (naphthalene 1-yl) -N ⁵ - phenyl ^-N 5, ^{N 9} - give the bis (4- (trimethylsilyl) phenyl)-7H-benzo [c] fluorene-5,9-diamine (4.1 g).

The structure of the compound represented by the formula (1-1-46) was confirmed by NMR measurement.
¹ H-NMR (CDCl ₃ ): δ = 8.64 (m, 1H), 8.09 (m, 1H), 8.03 (m, 1H), 7.96 (d, 1H), 7.90 (D, 1H), 7.80 (d, 1H), 7.38-7.56 (m, 5H), 7.26-7.37 (m, 7H), 7.19 (m, 2H), 6.90-7.18 (m, 8H), 0.24 (s, 9H), 0.22 (s, 9H).

  By appropriately selecting the starting compound, other benzofluorene compounds can be synthesized by a method according to the above synthesis example.

<Characteristics when used in electroluminescent devices>
Hereinafter, in order to describe the present invention in more detail, examples of the organic EL device using the compound of the present invention are shown, but the present invention is not limited thereto.

After the electroluminescent elements according to Examples 1 to 4 and Comparative Example 1 were manufactured and confirmed to emit light, the time during which the luminance was maintained at 90% or more of the initial value when driven at a constant current of 30 mA / cm ² was obtained. (Hr) was measured. Hereinafter, examples and comparative examples will be described in detail.

Table 1 below shows the material configuration of each layer in the fabricated elements according to Examples 1 to 4 and Comparative Example 1. In all cases, the cathode was composed of a co-deposited material of 8-quinolinol lithium (Liq) / magnesium and silver.

In Table 1, “HI” is N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine, “NPD” is N ⁴ , N ^{4 ′} -di (naphthalen-1-yl) -N ⁴ , N ^{4 ′} -diphenyl- [1,1′-biphenyl] -4,4′-diamine, compound (A) 9- (4- (naphthalen-1-yl) phenyl) -10-phenylanthracene, compound (B) is 7,7-dimethyl ^-N 5, ^{N 9} - diphenyl ^-N 5, ^{N 9} - Bis (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluorene-5,9-diamine, compound (C) is 4,4 ′-((2-phenylanthracene-9,10-diyl) bis (4 , 1-phenylene)) dipyridine. The chemical structure is shown below together with “Liq” used for the cathode.

<Example 1>
<Element Using Compound (1-1-11) for Light-Emitting Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing NPD, and compound (A) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (1-1-11), molybdenum vapor deposition boat containing compound (C), molybdenum vapor deposition boat containing Liq, magnesium A molybdenum vapor deposition boat and a tungsten vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 40 nm to form a hole injection layer, and then NPD entered. The vapor deposition boat was heated and vapor-deposited to a film thickness of 25 nm to form a hole transport layer. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (1-1-11) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 25 nm. The deposition rate was adjusted so that the weight ratio of the compound (A) to the compound (1-1-11) was approximately 95: 5. Next, the evaporation boat containing the compound (C) was heated and evaporated to a film thickness of 20 nm to form an electron transport layer. The above deposition rate was 0.01-1 nm / sec.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the cathode was formed so that the deposition rate was 0.1 nm to 10 nm, thereby obtaining 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 457 nm was obtained. Further, when a constant current driving test at 30 mA / cm ² was performed, the time for maintaining the luminance of 90% or more of the initial value was 80 hours.

<Example 2>
<Element Using Compound (1-2-11) for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1-11) was changed to the compound (1-2-11). 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. Further, when a constant current driving test at 30 mA / cm ² was performed, the time for maintaining the luminance of 90% or more of the initial value was 68 hours.

<Example 3>
<Element Using Compound (1-1-1) for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1-11) was changed to the compound (1-1-1). 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. Further, when a constant current driving test at 30 mA / cm ² was performed, the time for maintaining the luminance of 90% or more of the initial value was 75 hours.

<Example 4>
<Element Using Compound (1-2-1) for Light-Emitting Layer>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1-11) was changed to the compound (1-2-1). 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. Further, when a constant current driving test at 30 mA / cm ² was performed, the time for maintaining the luminance of 90% or more of the initial value was 94 hours.

<Comparative Example 1>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1-11) was changed to the compound (B). 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 458 nm was obtained. Further, when a constant current driving test of 30 mA / cm ² was performed, the time for maintaining the luminance of 90% or more of the initial value was 48 hours.

The above results are summarized in Table 2.

After the electroluminescent elements according to Example 5 and Comparative Example 2 were fabricated and each of which was confirmed to emit light, the time during which the luminance was maintained at 90% or more of the initial value when driven at a constant current of 30 mA / cm ² (hr ) Was measured.

Table 3 below shows the material configuration of each layer in the devices according to the manufactured Example 5 and Comparative Example 2. In all cases, the cathode was composed of a co-deposited material of 8-quinolinol lithium (Liq) / magnesium and silver.

  In Table 3, HT is N-([1,1′-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazol-3-yl) phenyl)- 9H-fluoren-2-amine, compound (D) is 9-phenyl-10- (4-phenylnaphthalen-1-yl) anthracene, and compound (E) is 2- (4- (9,10-di (naphthalene-) 2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [d] imidazole. The chemical structure is shown below.

<Example 5>
<Element Using Compound (1-1-46) for Light-Emitting Layer>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and a molybdenum vapor deposition boat containing HI, a molybdenum vapor deposition boat containing HT, and compound (D) are placed therein. Molybdenum vapor deposition boat, molybdenum vapor deposition boat containing compound (1-1-46), molybdenum vapor deposition boat containing compound (E), molybdenum vapor deposition boat containing Liq, magnesium A molybdenum vapor deposition boat and a tungsten vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber was depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI was heated to deposit to a film thickness of 40 nm to form a hole injection layer, and then HT entered. The vapor deposition boat was heated and vapor-deposited so that it might become a film thickness of 30 nm, and the positive hole transport layer was formed. Next, the vapor deposition boat containing the compound (D) and the vapor deposition boat containing the compound (1-1-46) were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of compound (D) to compound (1-1-46) was approximately 95: 5. Next, the vapor deposition boat containing the compound (E) and the vapor deposition boat containing Liq were heated at the same time so as to have a film thickness of 30 nm to form an electron transport layer. The deposition rate was adjusted so that the weight ratio of compound (E) to Liq was approximately 1: 1. The deposition rate of each layer was 0.01 to 1 nm / second.

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

When a direct current voltage was applied using the ITO electrode as the anode and the electrode made of the Liq / magnesium and silver co-deposited material as the cathode, blue light emission with a wavelength of about 455 nm was obtained. Further, when a constant current driving test at 30 mA / cm ² was performed, the time for maintaining the luminance of 90% or more of the initial value was 103 hours.

<Comparative example 2>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-1-46) was changed to the compound (B). When a direct current voltage was applied using the ITO electrode as the anode and the electrode made of the Liq / magnesium and silver co-deposited material as the cathode, blue light emission with a wavelength of about 455 nm was obtained. Further, when a constant current driving test of 30 mA / cm ² was performed, the time for maintaining the luminance of 90% or more of the initial value was 78 hours.

The above results are summarized in Table 4.

  As can be seen from the performance evaluation of the electroluminescent elements according to the examples and comparative examples described above, the electroluminescent elements according to the examples have improved lifetime characteristics than the electroluminescent elements according to the comparative examples.

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

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

Claims (16)

A benzofluorene compound represented by the following general formula (1).

In the above general formula,
R each independently represents alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 24 carbon atoms which may be substituted with alkyl having 1 to 4 carbon atoms, or carbon number A heteroaryl having 2 to 24 carbon atoms which may be substituted with 1 to 4 alkyls;
One of A and B is a group represented by the general formula (2), and the other is a group represented by the general formula (3).
R ¹ is each independently substituted with a hydrogen atom, a fluorine atom, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, an aryl having 6 to 10 carbon atoms, or an alkyl having 1 to 4 carbon atoms. Has been Cyril,
n is each independently an integer of 0 to 5, and
At least one hydrogen in the compound represented by the general formula (1) may be substituted with deuterium. The benzofluorene compound according to claim 1, which is represented by the following general formula (1-1).

In the general formula (1-1),
Each R is independently a C 1-6 alkyl, a C 3-6 cycloalkyl, or a C 6-12 aryl optionally substituted with a C 1-4 alkyl;
R ¹ is each independently substituted with a hydrogen atom, a fluorine atom, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, an aryl having 6 to 10 carbon atoms, or an alkyl having 1 to 4 carbon atoms. Being Cyril, and
n is an integer of 0-5 each independently. The benzofluorene compound according to claim 1, which is represented by the following general formula (1-2).

In the general formula (1-2),
Each R is independently a C 1-6 alkyl, a C 3-6 cycloalkyl, or a C 6-12 aryl optionally substituted with a C 1-4 alkyl;
R ¹ is each independently substituted with a hydrogen atom, a fluorine atom, an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, an aryl having 6 to 10 carbon atoms, or an alkyl having 1 to 4 carbon atoms. Being Cyril, and
n is an integer of 0-5 each independently. Each R is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclohexyl, phenyl or naphthyl;
Each R ¹ independently represents a hydrogen atom, a fluorine atom, methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl, triethylsilyl or dimethylmono; t-butylsilyl and
n is each independently an integer of 0 to 2,
The benzofluorene compound according to claim 2 or 3. Each R is independently methyl, ethyl, isopropyl, s-butyl, t-butyl, or phenyl;
Each R ¹ is independently a hydrogen atom, a fluorine atom, methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl or trimethylsilyl, and
n is each independently an integer of 0 to 2,
The benzofluorene compound according to claim 2 or 3. The benzofluorene compound according to claim 1, which is represented by the following formula (1-1-11).

In the above formula, TMS represents trimethylsilyl. The benzofluorene compound according to claim 1, which is represented by the following formula (1-2-11).

In the above formula, TMS represents trimethylsilyl. The benzofluorene compound according to claim 1, which is represented by the following formula (1-2-1).

The benzofluorene compound according to claim 1, which is represented by the following formula (1-1-1).

The benzofluorene compound according to claim 1, which is represented by the following formula (1-1-46).

  A material for a light emitting layer of a light emitting element, the material for a light emitting layer containing the benzofluorene compound according to any one of claims 1 to 10.   The organic electroluminescent element which has a pair of electrode which consists of an anode and a cathode, and the light emitting layer which is arrange | positioned between this pair of electrodes and contains the material for light emitting layers of Claim 11.   Furthermore, it has an electron transport layer and / or an electron injection layer disposed between the cathode and the light emitting layer, and at least one of the electron transport layer and the electron injection layer includes a quinolinol-based metal complex, a pyridine derivative, The organic electroluminescent device according to claim 12, comprising at least one selected from the group consisting of a phenanthroline derivative, a borane derivative, and a benzimidazole derivative.   The electron transport layer and / or the electron injection layer further includes an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, or an alkaline earth metal. The material contains at least one selected from the group consisting of halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes. 14. The organic electroluminescent element according to 13.   A display device comprising the organic electroluminescent element according to claim 12.   A lighting device comprising the organic electroluminescent element according to claim 12.

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