JP2012067077A - Anthracene derivative and organic electroluminescent device using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel anthrathene derivative useful as an organic electroluminescent device excellent in the life and the drive voltage of the luminescent device; and to provide an electron transport material and an organic electroluminescent device containing the derivative.SOLUTION: There are provided an anthrathene derivative represented by formula (1), and an electron transport material and an organic electroluminescent device containing the derivative. In the formula, A and B are each independently a pyridylphenyl group and/or a pyridylnaphthyl group, and do not have the same structure; Rto Rare each independently hydrogen, a 1-6C alkyl, a 3-6C cycloalkyl, or a 6-20C aryl which may be substituted.

Description

  The present invention relates to an anthracene derivative and an organic electroluminescent element, a display device, and a lighting device using the anthracene derivative.

  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.

  For example, an organic electroluminescent device using a compound in which a pyridylphenyl group is substituted on the central skeleton of anthracene has been reported (Japanese Patent Laid-Open No. 2009-173642 (Patent Document 1), Japanese Patent Laid-Open No. 2005-170911 (Patent Document). 2)). In addition, an organic electroluminescence device using a compound in which a bipyridyl group is substituted on the central skeleton of anthracene has been reported (Re-Table 2007/086552 (Patent Document 3)).

JP 2009-173642 A Japanese Unexamined Patent Publication No. 2005-170911 No. 2007/086552 gazette

  As described above, several materials for light emitting devices of compounds in which the central skeleton of anthracene is substituted with a pyridylphenyl group or a bipyridyl group are known, but these known materials are used for improving the heat resistance. The skeleton has a substituent other than the substitution position where the pyridylphenyl group or bipyridyl group is substituted. As a result, the energy gap is reduced by the amount of the substituent, and the confinement effect of excitons in the light emitting layer, which is generally required for electron transport materials, is not sufficient in blue elements. Therefore, it cannot be said to be an electron transport material suitable for improving the characteristics of the blue light-emitting element that is particularly desired, and the development of an excellent electron transport material having a wider energy gap is desired.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an anthracene derivative represented by the following formula (1) as an electron transporting material in order to obtain an organic electroluminescent device having improved characteristics particularly in a blue device. It has been found that it is effective to provide an organic layer to be contained, and the present invention has been completed. The present invention is constituted by the following items.

上記式（１）中、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４は、それぞれ独立して、水素、炭素数１〜６のアルキル、炭素数３から６のシクロアルキル、または置換されていてもよい炭素数６〜２０のアリールであり、ＡおよびＢは、それぞれ独立して、下記式（Ｐｙ−１）〜式（Ｐｙ−１２）のいずれかで表される基であり、ただし、ＡおよびＢは同一構造ではない。

[1] An anthracene derivative represented by the following formula (1).

In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, or substituted Good aryl having 6 to 20 carbon atoms, and A and B are each independently a group represented by any of the following formulas (Py-1) to (Py-12), provided that A and B is not the same structure.

[2] In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and A and B are each independently the above formula (Py-1) to formula (Py-12). The anthracene derivative according to [1] above, wherein A and B are not the same structure.

[3] In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and one of A and B is represented by the above formula (Py-1) to formula (Py-9). The other is a group represented by any one of the above formulas (Py-1) to (Py-12), provided that A and B are not the same structure, The anthracene derivative described in [1].

[4] In the formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and one of A and B is represented by the formula (Py-1) to the formula (Py-3). The anthracene derivative according to the above [1], which is a group represented by any one and the other is a group represented by any one of the above formulas (Py-4) to (Py-12).

[5] In the formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and one of A and B is represented by the formula (Py-4) to the formula (Py-9). The anthracene derivative according to the above [1], which is a group represented by any one and the other is a group represented by any one of the above formulas (Py-7) to (Py-12).

[6] The anthracene derivative according to [1], which is represented by the following formula (1-6).

[7] The anthracene derivative according to [1], which is represented by the following formula (1-11).

[8] The anthracene derivative according to the above [1], which is represented by the following formula (1-15).

[9] The anthracene derivative according to the above [1], represented by the following formula (1-19).

[10] The anthracene derivative according to the above [1], which is represented by the following formula (1-24).

[11] The anthracene derivative according to the above [1], represented by the following formula (1-36).

[12] The anthracene derivative according to the above [1], which is represented by the following formula (1-27).

[13] The anthracene derivative according to [1], which is represented by the following formula (1-42).

[14] The anthracene derivative according to the above [1], represented by the following formula (1-54).

[15] An electron transport material containing the anthracene derivative according to any one of [1] to [14].

[16] A pair of electrodes composed of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport material according to the above [15] disposed between the cathode and the light emitting layer. An organic electroluminescent device having an electron transport layer and / or an electron injection layer.

[17] At least one of the electron transport layer and the electron injection layer further includes at least one selected from the group consisting of a quinolinol-based metal complex, a pyridine derivative, a bipyridine derivative, a phenanthroline derivative, a borane derivative, and a benzimidazole derivative. The organic electroluminescent element according to [16], which is contained.

[18] At least one of the electron transport layer and the electron injection layer may further include an alkali metal, an alkaline earth metal, a rare earth metal, an alkali metal oxide, an alkali metal halide, an alkaline earth metal oxide, At least one selected from the group consisting of alkaline earth metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes The organic electroluminescent element as described in the above [15] or [17].

[19] A display device comprising the organic electroluminescent element as described in any one of [16] to [18].

[20] An illumination device including the organic electroluminescent element according to any one of [16] to [18].

  According to a preferred embodiment of the present invention, a stable electron transport layer and / or electron injection layer can be formed by using an anthracene derivative having low crystallinity and capable of forming a stable amorphous film. A stable light-emitting element can be manufactured. Further, according to a preferred embodiment of the present invention, by using an anthracene derivative having a molecular structure with a wide energy gap, the effect of confining excitons in the light emitting layer, which is generally required for electron transport materials, is improved. An electron transport material suitable for improving the characteristics of the blue light-emitting element can be provided. Furthermore, since a blue light-emitting element having an element lifetime comparable to that of a red or green light-emitting element can be manufactured, a high-performance display device such as a full-color display can be obtained.

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

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

R ¹ , R ² , R ³ and R ⁴ (hereinafter also referred to as “R ^{1 to} R ⁴ ”) in the formula (1) are each independently hydrogen, alkyl having 1 to 6 carbons, 3 to 3 carbons It can be appropriately selected from 6 cycloalkyl or optionally substituted aryl having 6 to 20 carbon atoms.

About C1-C6 alkyl in R < ¹ > -R < ⁴ > of Formula (1), C1-C6 alkyl may be any of a straight chain and a branched chain. That is, it is a linear alkyl having 1 to 6 carbon atoms or a branched alkyl having 3 to 6 carbon atoms. More preferred is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms). Specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl and the like are listed, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, or t-butyl is preferable. More preferred are methyl, ethyl, or t-butyl.

Specific examples of the cycloalkyl having 3 to 6 carbon atoms in R ^{1 to} R ⁴ of the formula (1) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl. can give.

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

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

  Preferred “C6-C20 aryl” is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5′-yl; More preferred is phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, and most preferred is phenyl.

Examples of the “substituent” that may be substituted with the “aryl having 6 to 20 carbon atoms” of R ^{1 to} R ^{4 in} the formula (1) include alkyl, and preferred examples thereof include those in R ^{1 to} R ⁴ . Examples thereof are the same as those described in the “alkyl” column.

Specific examples of the “substituent” which may be substituted with “aryl having 6 to 20 carbon atoms” of R ^{1 to} R ⁴ include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s -Butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, etc. It is done. The number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1. However, unsubstituted is most preferred.

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

The anthracene derivative according to the present invention has an asymmetric molecular structure without forming A and B in the formula (1) as the same structure as described later, thereby forming an organic layer in an organic electroluminescence device. This material is expected to have an effect of disturbing crystallization by disturbing the regularity of the arrangement of molecules. Therefore, R ^{1 to} R ⁴ may all be the same or different, but in addition to this effect, considering that they can be produced by a simple method, R ^{1 to} R ⁴ are hydrogen, methyl, ethyl, A compound in which t-butyl and phenyl are used, particularly a compound in which R ^{1 to} R ⁴ are hydrogen and methyl is preferable, and a compound in which all of R ^{1 to} R ⁴ are hydrogen in consideration of further widening the energy gap. Is preferred.

  A and B are each independently groups represented by the following formula (Py-1) to formula (Py-12), provided that A and B are not the same structure. The main purpose of making A and B different structures is to make the anthracene derivative an asymmetric molecular structure and reduce the crystallinity.

  The combination of A and B is not particularly limited as long as it is not the same structure, but the group of formula (Py-1) to formula (Py-3), formula (Py-4) to formula (Py-6). ), Group of formula (Py-7) to formula (Py-9), and group of formula (Py-10) to formula (Py-12) are considered as four groups, A and B are the same. You may choose from a group. In this case, an asymmetric molecular structure is formed by different positions of nitrogen atoms in the pyridine ring. However, more preferably, A and B are selected from different groups to form a molecular structure having greater asymmetry.

  As a combination of A and B, it is further preferable that one of A and B is a group selected from Formula (Py-1) to Formula (Py-6). This is because among the groups represented by the formulas (Py-1) to (Py-12), the groups represented by the formulas (Py-1) to (Py-6) were substituted with anthracene derivatives. This is because in some cases, it has a structure that can greatly break the symmetry of the molecular structure.

  Of these, when one of A and B is selected from the formula (Py-1) to the formula (Py-3), the other is selected from the formula (Py-4) to the formula (Py-12). Is preferred. This is because, as described above, it is preferable to select A and B from different groups to obtain a molecular structure having a greater asymmetry. In one embodiment of the present invention, the other is a group selected from Formula (Py-4) to Formula (Py-9), and in another embodiment, the other is Formula (Py-7). The case where it is group chosen from-formula (Py-9) is mention | raise | lifted.

  Of these, when one of A and B is selected from the formula (Py-4) to the formula (Py-6), the other is the formula (Py-1) to the formula (Py-3), formula The case selected from (Py-7) to formula (Py-12) is preferred. This is because, as described above, it is preferable to select A and B from different groups to obtain a molecular structure having a greater asymmetry. In one embodiment of the present invention, the other is a group selected from Formula (Py-7) to Formula (Py-9).

  The above is a preferable form examined from the viewpoint of the asymmetry of the molecular structure. From further research, in addition to making A and B different structures, the formula (Py-3) and the formula (Py-6) It has been found that it is preferable to select groups represented by formulas (Py-9) and (Py-12), that is, groups having 4-pyridyl at the terminal.

  In one embodiment of the present invention, neither A nor B is selected from the group of formula (Py-4) to formula (Py-6). In one embodiment of the present invention, neither A nor B is selected from the group of formula (Py-10) to formula (Py-12).

  Specific examples of the anthracene derivative represented by the above formula (1) include anthracene derivatives represented by the following formulas (1-1) to (1-66). Among these, anthracene derivatives represented by the following formulas (1-1) to (1-54) are preferable. More preferred are anthracene derivatives represented by the following formulas (1-1) to (1-45).

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

  When producing the anthracene derivative of the present invention, (1) a method of synthesizing a group in which an end group and an intermediate group are bonded, and bonding this to the 9,10-position of anthracene, (2) 9,9 of anthracene An example is a method in which an intermediate group is bonded to the 10-position and a terminal group is bonded to this intermediate group. In addition, in these methods, the bond between the intermediate group and the terminal group or the bond between the anthracene and the intermediate group basically includes a halogen functional group or a trifluoromethanesulfonate functional group, a zinc chloride complex, or a boronic acid (boron). A coupling reaction with an acid ester) can be used.

(1) A method of attaching a “terminal-intermediate” group to the 9,10-position of anthracene
<"Terminal-intermediate" group: Synthesis of pyridylphenyl having a reactive substituent>
First, a zinc chloride complex of pyridine is synthesized according to the following reaction formula (1), and then a zinc chloride complex of pyridine and m-dibromobenzene are reacted according to the following reaction formula (2) to thereby give 2- (3-bromophenyl). ) Pyridine can be synthesized. In the reaction formula (1), “ZnCl ₂ · TMEDA” is a tetramethylethylenediamine complex of zinc chloride. In “RLi” and “RMgX” in the reaction formula (1), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. And X is a halogen.

  Here, the synthesis method using 2-bromopyridine as the raw material of the end group is illustrated, but it can be handled by using 3-bromopyridine or 4-bromopyridine as the raw material, and using iodide instead of bromide. The target object to be obtained can be obtained.

  Moreover, although the synthesis method using m-dibromobenzene as an intermediate group raw material has been exemplified here, by using p-dibromobenzene, 1,4-dibromonaphthalene, 2,6-dibromonaphthalene as a raw material, The corresponding target product can also be obtained by using dichloro, diiodo, bis (trifluoromethanesulfonate) or a mixture thereof (for example: 1-bromo-3-iodobenzene, etc.) instead of dibromo. . Also, like bromoanisole, a benzene or naphthalene derivative having a halogen atom and an alkoxy group as a substituent is reacted with a zinc chloride complex of pyridine, followed by demethylation using boron tribromide or pyridine hydrochloride. Then, the desired product can also be obtained through trifluoromethanesulfonic acid esterification.

  Moreover, the said target object can be obtained also by the coupling reaction which makes pyridyl boronic acid and a pyridyl boronic ester react instead of making the zinc chloride complex of a pyridine react with m-dibromobenzene.

<Method for Converting Reactive Substituent into Boronic Acid / Boronate Ester>
According to the following reaction formula (3), 2- (3-bromophenyl) pyridine is lithiated using an organolithium reagent or converted to a Grignard reagent using magnesium or an organomagnesium reagent, and trimethyl borate, triethyl borate or By reacting with triisopropyl borate or the like, (3- (pyridin-2-yl) phenyl) boronic acid ester can be synthesized. Further, according to the following reaction formula (4), (3- (pyridin-2-yl) phenyl) boronic acid is synthesized by hydrolyzing the (3- (pyridin-2-yl) phenyl) boronic acid ester. be able to. In “RLi” and “RMgX” in the reaction formula (3), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. And X is a halogen.

  Further, according to the following reaction formula (5), 2- (3-bromophenyl) pyridine is lithiated using an organolithium reagent, or converted into a Grignard reagent using magnesium or an organomagnesium reagent, and bis (pinacolato) diboron or Other 3- (pyridin-2-yl) phenyl) boronic acid esters can be synthesized by reacting with 4,4,5,5-tetramethyl-1,3,2-dioxaborolane. Further, according to the following reaction formula (6), 2- (3-bromophenyl) pyridine and bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane are combined with a palladium catalyst. A similar 2,2′-bipyridineboronic acid ester can be synthesized by a coupling reaction using a base. In “RLi” and “RMgX” in the reaction formula (5), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. And X is a halogen.

  In the above reaction formula (3), (5) or (6), the corresponding boronic acid / boronic acid ester is synthesized even if other positional isomers are used instead of 2- (3-bromophenyl) pyridine. be able to. Furthermore, it can be similarly synthesized by using chloride, iodide or trifluoromethanesulfonate instead of bromide such as 2- (3-bromophenyl) pyridine.

<Synthesis of a central skeleton anthracene having a reactive substituent>
<9,10-Dibromoanthracene>
As shown in the following reaction formula (7), 9,10-dibromoanthracene is obtained by brominating anthracene using an appropriate brominating agent. Suitable brominating agents include bromine or N-brominated succinimide (NBS).

  When an anthracene derivative having a substituent (alkyl, cycloalkyl, aryl, etc.) at the 2-position is desired, anthracene substituted at the 2-position with a halogen or triflate and a boronic acid of a group corresponding to the substituent (or Anthracene derivatives having a substituent at the 2-position can be synthesized by Suzuki coupling with boronic acid ester). Another method is a synthesis method by Negishi coupling between anthracene substituted at the 2-position with halogen or triflate and a zinc complex of a group corresponding to the substituent. Further, a synthesis method by Suzuki coupling of 2-anthraceneboronic acid (or boronate ester) and a group corresponding to the substituent substituted with halogen or triflate, and further, with 2-anthracene zinc complex and halogen or triflate A synthesis method by Negishi coupling with a group corresponding to the substituted group is also included. For anthracene derivatives having a substituent other than the 2-position, similarly, by using a raw material in which the position of halogen, triflate, boronic acid (or boronic acid ester) or zinc complex to be substituted for anthracene is set to a desired position, Can be synthesized.

<9,10-dianthracene zinc complex>
As shown in the following reaction formula (8), 9,10-dibromoanthracene is lithiated using an organic lithium reagent, or converted to a Grignard reagent using magnesium or an organic magnesium reagent, and zinc chloride or zinc chloride tetramethylethylenediamine is used. A 9,10-dianthracene zinc complex can be synthesized by reacting with the complex (ZnCl ₂ · TMEDA). In Reaction Formula (8), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. In addition, it can synthesize | combine similarly even if it uses a chloride or an iodide instead of bromide like 9,10- dibromoanthracene.

<9,10-anthracene diboronic acid (or boronic ester)>
As shown in the following reaction formula (9), 9,10-dibromoanthracene is lithiated using an organolithium reagent, or converted to a Grignard reagent using magnesium or an organomagnesium reagent, and trimethyl borate, triethyl borate or By reacting with triisopropyl borate or the like, 9,10-anthracene diboronic acid ester can be synthesized. Furthermore, 9,10-anthracene diboronic acid can be synthesized by hydrolyzing the 9,10-anthracene diboronic acid ester in the following reaction formula (10). In the reaction formula (9), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  Further, as shown in the following reaction formula (11), 9,10-dibromoanthracene is lithiated using an organolithium reagent, or converted to a Grignard reagent using magnesium or an organomagnesium reagent, and bis (pinacolato) diboron or Other 9,10-anthracene diboronic acid esters can be synthesized by reacting with 4,4,5,5-tetramethyl-1,3,2-dioxaborolane. Further, as shown in the following reaction formula (12), 9,10-dibromoanthracene and bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane are combined with a palladium catalyst. A similar 9,10-anthracene diboronic acid ester can be synthesized by a coupling reaction using a base. In Reaction Formula (11), R represents a linear or branched alkyl group, preferably a linear or branched alkyl group having 1 to 4 carbon atoms.

  In the above reaction formula (9), (11) or (12), the same synthesis can be performed by using chloride, iodide or triflate instead of bromide such as 9,10-dibromoanthracene. it can.

<Method for Bonding Substituent Anthracene to “Terminal-Intermediate” Group>
As described above, for the “terminal-intermediate” group, a bromo form of pyridylphenyl (reaction formulas (1) to (2)), a boronic acid, a boronic acid ester (reaction formulas (3) to (6)), As for the anthracene which can be synthesized and has a substituent, bromo form of anthracene (reaction formula (7)), zinc chloride complex (reaction formula (8)), boronic acid, boronate ester (reaction formula (9) to (12)) can be synthesized, and the anthracene derivative of the present invention is synthesized by linking the “terminal-intermediate” group and anthracene with reference to the coupling reaction used in the above description. Can do.

  In this final coupling reaction, in order to make A and B of the anthracene derivative represented by the formula (1) different structures, first, anthracene having a substituent and a “terminal-intermediate” group equivalent to 1 mole Then, this intermediate is reacted with a compound having a different “terminal-intermediate” group (ie, reacted in two steps).

(2) A method of attaching an end group to an anthracene having an intermediate group bonded to the 9 and 10 positions In this method as well, referring to the various coupling reactions described above, an intermediate group is first bonded to the 9 and 10 positions of anthracene. And an end group may be bonded to the intermediate group. At this time, in order to make A and B of the anthracene derivative represented by the formula (1) different structures, different intermediate groups may be bonded in a two-step reaction in the step of bonding the intermediate group to the anthracene, A desired anthracene derivative can be synthesized by, for example, linking different terminal groups in a two-step reaction in the step of bonding the terminal group to the.

<About the reagents used in the reaction>
Specific examples of the palladium catalyst used in the coupling reaction include Pd (PPh ₃ ) ₄ , PdCl ₂ (PPh ₃ ) ₂ , Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0), tris (di) Benzylideneacetone) dipalladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0), bis (tri-t-butylphosphino) palladium (0), or (1,1′-bis (diphenylphosphino) ferrocene ) Dichloropalladium (II).

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

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

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

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

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

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

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

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

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

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

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

  The resistance of the transparent electrode is not limited as long as it can supply a sufficient current for light emission of the light emitting element, but is preferably low resistance from the viewpoint of power consumption of the light emitting element. For example, an ITO substrate of 300Ω / □ or less functions as an element electrode. However, since it is now possible to supply a substrate of about 10Ω / □, for example, 100-5Ω / □, preferably 50-5Ω. It is particularly desirable to use a low resistance product of / □. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 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 group in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl)- 4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di (3-methylphenyl)- 4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl- , 1′-diamine, 4,4 ′, 4 ″ -tris (3-methylphenyl (phenyl) amino) triphenylamine, and the like, starburstamine derivatives, and the like, stilbene derivatives, phthalocyanine derivatives (metal-free, Copper phthalocyanine), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, heterocyclic compounds such as oxadiazole derivatives, porphyrin derivatives, polysilanes, etc. Styrene derivatives, polyvinyl carbazole, polysilane, and the like are preferable, but there is no particular limitation as long as it is a compound that forms a thin film necessary for manufacturing a light-emitting element, can inject holes from the anode, and can further transport holes. .

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

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

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

  The amount of the host material used varies depending on the type of the host material, and may be determined according to the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999% by weight of the entire light emitting material, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight. .

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

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

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

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

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

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

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

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

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

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

Examples of perylene derivatives include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, 3,10-diphenylperylene, 3,4- Diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene 3- (9′-anthryl) -8,11-di (t-butyl) perylene, 3,3′-bis (8,11-di (t-butyl) perylenyl), and the like.
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'-bis ( -Ethyl-3-carbazovinylene) -biphenyl, 4,4′-bis (9-phenyl-3-carbazovinylene) -biphenyl, etc. In addition, JP 2003-347056 A and JP 2001-307884 A Amine-containing styryl derivatives described in the above may be used.

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

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

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.

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

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

As a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, a compound represented by the above formula (1) can be used. Of these, anthracene derivatives represented by the above formulas (1-1) to (1-66) are preferable.
The content of the anthracene derivative represented by the above formula (1) in the electron transport layer 106 or the electron injection layer 107 differs depending on the type of the derivative and may be determined according to the characteristics of the derivative. The standard of the content of the anthracene derivative represented by the above formula (1) is preferably 1 to 100% by weight, more preferably 10 to 100% of the whole electron transport layer material (or electron injection layer material). % By weight, more preferably 50 to 100% by weight, and particularly preferably 80 to 100% by weight. When the anthracene derivative represented by the above formula (1) is not used alone (100% by weight), other materials described in detail below may be mixed.

  Other materials for forming the electron transport layer or electron injection layer include compounds conventionally used as electron transport compounds in photoconductive materials, and known materials used for electron injection layers and electron transport layers of organic electroluminescent devices. Any of these compounds can be selected and used.

  Materials used for the electron transport layer or the electron injection layer include compounds composed of aromatic rings or heteroaromatic rings composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, and pyrrole derivatives. And at least one selected from the condensed ring derivatives thereof and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4′-bis (diphenylethenyl) biphenyl, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinones And quinone derivatives such as diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. These materials can be used alone or in combination with different materials. Among them, anthracene derivatives such as 9,10-bis (2-naphthyl) anthracene, styryl aromatic ring derivatives such as 4,4′-bis (diphenylethenyl) biphenyl, 4,4′-bis (N-carbazolyl) biphenyl A carbazole derivative such as 1,3,5-tris (N-carbazolyl) benzene is preferably used from the viewpoint of durability.

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

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

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

  Among the materials described above, quinolinol metal complexes, bipyridine 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 bipyridine derivative is a compound represented by the following general formula (E-2).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  Examples of the illuminating device include an illuminating device such as indoor lighting, a backlight of a liquid crystal display device, and the like (for example, JP 2003-257621 A, JP 2003-277741 A, JP 2004-119211 A). Etc.) The backlight is used mainly for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a clock, an audio device, an automobile panel, a display board, 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.

  Hereinafter, the present invention will be described in more detail based on examples. First, synthesis examples of anthracene derivatives used in the examples are described below.

<Synthesis Example of Anthracene Derivative Represented by Formula (1-6)>

<Synthesis of 4- (4- (anthracen-9-yl) phenyl) pyridine>
9-bromoanthracene (25.0 g), bispinacolatodiboron (27.0 g), Pd (dba) ₂ (1.7 g), tricyclohexylphosphine (1.6 g), potassium acetate (19.0 g), carbonic acid A flask containing potassium (14.0 g) and cyclopentyl methyl ether (200 ml) was heated and stirred at reflux temperature for 10 hours. Once cooled to room temperature, 4- (4-bromophenyl) pyridine (27.0 g), Pd (PPh ₃ ) ₄ (2.2 g) and 1,2,4-trimethylbenzene (200 ml) were added and the reflux temperature was increased. The mixture was further stirred with heating for 2 hours. After the reaction solution was cooled to room temperature, the target product was extracted with chlorobenzene. In this chlorobenzene solution, an ethylenediaminetetraacetic acid / tetrasodium salt dihydrate equivalent to approximately equimolar amounts of the target compound was dissolved in an appropriate amount of water (hereinafter referred to as EDTA · The solution was abbreviated as 4Na aqueous solution. The solvent was distilled off under reduced pressure, and the precipitated solid was washed with methanol. Further, it was dissolved again in chlorobenzene and purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, referring to the method described in “Chemical Doujin Shuppan Co., Ltd., page 94”, the ratio of ethyl acetate in the developing solution was gradually increased. The target product was eluted by increasing the amount to 1. After the solvent was distilled off under reduced pressure, the residue was washed with methanol to obtain 4- (4- (anthracen-9-yl) phenyl) pyridine (15.9 g).

<Synthesis of 4- (4- (10-bromoanthracen-9-yl) phenyl) pyridine>
A flask containing 4- (4- (anthracen-9-yl) phenyl) pyridine (8.0 g), N-bromosuccinimide (4.5 g), iodine (0.06 g) and chloroform (500 ml) was stirred at room temperature. For 18 hours. A sodium sulfite aqueous solution was added to stop the reaction, and then the solution was distilled off under reduced pressure. The precipitated solid was washed with methanol, then water, and methanol, and then dissolved in chlorobenzene. Methanol was added to this solution and reprecipitated to obtain 4- (4- (10-bromoanthracen-9-yl) phenyl) pyridine (9.1 g).

<Synthesis of Compound Represented by Formula (1-6)>
2- (3-bromophenyl) pyridine (2.8 g), bispinacolatodiboron (3.3 g), Pd (dppf) Cl ₂ (0.3 g), potassium acetate (3.5 g) and cyclopentyl methyl ether ( The flask containing 20 ml) was heated and stirred at reflux temperature for 2 hours. Once cooled to room temperature, 4- (4- (10-bromoanthracen-9-yl) phenyl) pyridine (4.1 g), Pd (dba) ₂ (0.17 g), tricyclohexylphosphine (0.17 g) , Potassium phosphate (6.4 g), t-butyl alcohol (1 ml) and 1,2,4-trimethylbenzene (50 ml) were added, and the mixture was further heated and stirred at reflux temperature for 2 hours. After cooling the reaction solution to room temperature, the solid in the solution was collected by suction filtration, and washed with methanol, then water, and methanol. After washing, the product was purified by silica gel column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The solvent was distilled off under reduced pressure, and then recrystallized from chlorobenzene to obtain a compound (3.1 g) represented by the formula (1-6).

The glass transition temperature (Tg) determined by DSC measurement was 115 ° C., and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.95 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.75 (m, 2H), 8.71 (d, 1H), 8.25 (d, 1H), 8.11 (m, 1H), 7.91 (D, 2H), 7.71-7.81 (m, 8H), 7.70 (m, 2H), 7.63 (m, 2H), 7.56 (d, 1H), 7.37 ( m, 4H).

<Synthesis Example of Anthracene Derivative Represented by Formula (1-11)>

<Synthesis of 3- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalen-1-yl) pyridine>
3- (4-bromonaphthalen-1-yl) pyridine (29.8 g), bispinacolatodiboron (5.5 g), Pd (dppf) Cl ₂ (3.2 g), potassium acetate (28.0 g) and The flask containing cyclopentyl methyl ether (60 ml) was stirred with heating at reflux temperature for 1.5 hours. After cooling to room temperature, toluene and an EDTA · 4Na aqueous solution were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was purified by activated carbon column chromatography (developing solution: toluene), and 3- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) was purified. ) Naphthalen-1-yl) pyridine (30.1 g) was obtained.

<Synthesis of 3- (4- (anthracen-9-yl) naphthalen-1-yl) pyridine>
3- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) naphthalen-1-yl) pyridine (5.3 g), 9-bromoanthracene (4.9 g) ), Pd (dba) ₂ (0.3 g), tricyclohexylphosphine (0.3 g), potassium phosphate (6.8 g) and 1,2,4-trimethylbenzene (30 ml) were added to the reflux temperature. And stirred for 13 hours. After cooling to room temperature, toluene and water were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate mixed solvent) to give 3- (4- (anthracen-9-yl) naphthalen-1-yl) pyridine (4.1 g). ) At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The solvent was removed under reduced pressure.

<Synthesis of 3- (4- (10-bromoanthracen-9-yl) naphthalen-1-yl) pyridine>
Contains 3- (4- (anthracen-9-yl) naphthalen-1-yl) pyridine (1.9 g), N-bromosuccinimide (1.1 g), iodine (0.001 g) and THF (20 ml). The flask was stirred at room temperature for 18 hours. An aqueous sodium thiosulfate solution was added to stop the reaction, and toluene was added to separate the layers. After distilling off the solution under reduced pressure, the residue was purified with a silica gel short column (developing solution: toluene / ethyl acetate mixed solvent (volume ratio = approximately 1/1)) to give 3- (4- (10-bromoanthracen-9-yl). Naphthalen-1-yl) pyridine (2.2 g) was obtained.

<Synthesis of 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine>
3- (3-bromophenyl) pyridine (18.0 g), bispinacolatodiboron (23.4 g), Pd (dppf) Cl ₂ (1.9 g), potassium acetate (20.5 g) and cyclopentyl methyl ether ( 150 ml) was heated and stirred at reflux temperature for 1 hour. After cooling to room temperature, toluene and an EDTA · 4Na aqueous solution were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was purified by activated carbon column chromatography (developing solution: toluene), and 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) was purified. ) Phenyl) pyridine (6.5 g) was obtained.

<Synthesis of Compound Represented by Formula (1-11)>
3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) pyridine (1.4 g), 3- (4- (10-bromoanthracene-9) -Yl) naphthalen-1-yl) pyridine (1.8 g), Pd (PPh ₃ ) ₄ (0.1 g), potassium phosphate (1.7 g), 1,2,4-trimethylbenzene (20 ml), isopropyl A flask containing alcohol (2 ml) and water (2 ml) was heated and stirred at reflux temperature for 9 hours. After cooling to room temperature, toluene and water were added for liquid separation. After the solvent was distilled off under reduced pressure, the residue was purified by activated alumina column chromatography (developing solution: toluene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The solvent was distilled off under reduced pressure, and then recrystallized from toluene to obtain a compound (0.3 g) represented by the formula (1-11).

The glass transition temperature (Tg) determined by DSC measurement was 130 ° C., and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.97 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 9.00 (m, 2H), 8.77 (dd, 1H), 8.62 (td, 1H), 8.00 (m, 3H), 7.75 -7.85 (m, 6H), 7.45-7.68 (m, 7H), 7.25-7.40 (m, 6H).

<Synthesis Example of Anthracene Derivative Represented by Formula (1-15)>

3- (3-bromophenyl) pyridine (5.6 g), bispinacolato diboron (6.6 g), Pd (dppf) Cl ₂ (0.6 g), potassium acetate (7.0 g) and cyclopentyl methyl ether ( 40 ml) was heated and stirred at reflux temperature for 2 hours. Once cooled to room temperature, 4- (4- (10-bromoanthracen-9-yl) phenyl) pyridine (8.0 g), Pd (dba) ₂ (0.34 g), tricyclohexylphosphine (0.33 g) , Potassium phosphate (12.4 g), t-butyl alcohol (1 ml) and 1,2,4-trimethylbenzene (100 ml) were added, and the mixture was further heated and stirred at reflux temperature for 5 hours. After cooling the reaction solution to room temperature, the solid in the solution was collected by suction filtration, and washed with methanol, then water, and methanol. After washing, it was purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The solvent was distilled off under reduced pressure, and then recrystallized from chlorobenzene to obtain a compound (7.0 g) represented by the formula (1-15).

The glass transition temperature (Tg) determined by DSC measurement was 111 ° C., and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.94 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.97 (m, 1H), 8.76 (m, 2H), 8.61 (dd, 1H), 7.98 (m, 1H), 7.92 (D, 2H), 7.73-7.82 (m, 7H), 7.70 (m, 2H), 7.62 (m, 2H), 7.56 (d, 1H), 7.39 ( m, 5H).

<Synthesis Example of Anthracene Derivative Represented by Formula (1-19)>

<Synthesis of 4- (3- (anthracen-9-yl) phenyl) pyridine>
9-bromoanthracene (25.0 g), bispinacolatodiboron (27.0 g), Pd (dba) ₂ (2.8 g), tricyclohexylphosphine (2.7 g), potassium acetate (19.0 g), carbonic acid A flask containing potassium (14.0 g) and cyclopentyl methyl ether (200 ml) was heated and stirred at reflux temperature for 12 hours. Once cooled to room temperature, 4- (3-bromophenyl) pyridine (27.0 g), Pd (PPh ₃ ) ₄ (3.3 g), t-butyl alcohol (20 ml) and 1,2,4-trimethylbenzene (200 ml) was added, and the mixture was further heated and stirred at reflux temperature for 8 hours. After cooling the reaction solution to room temperature, the precipitated solid was removed by suction filtration, and an EDTA · 4Na aqueous solution was added to separate the layers. The oil obtained by distilling off the solvent under reduced pressure was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate mixed solvent) to give 4- (3- (anthracen-9-yl) phenyl) pyridine (24.6 g). ) At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution.

<Synthesis of 4- (3- (10-bromoanthracen-9-yl) phenyl) pyridine>
A flask containing 4- (3- (anthracen-9-yl) phenyl) pyridine (23.6 g), N-bromosuccinimide (13.3 g), iodine (0.09 g) and chloroform (500 ml) was stirred at room temperature. For 18 hours. A sodium sulfite aqueous solution was added and the layers were separated, and the solution was evaporated under reduced pressure. The obtained oil was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate mixed solvent) to give 4- (3- (10- Bromoanthracen-9-yl) phenyl) pyridine (26.6 g) was obtained. At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution.

<Synthesis of Compound Represented by Formula (1-19)>
2- (4-bromonaphthalen-1-yl) pyridine (6.8 g), bispinacolatodiboron (6.1 g), Pd (dppf) Cl ₂ (0.6 g), potassium acetate (7.1 g) and A flask containing cyclopentyl methyl ether (50 ml) was heated and stirred at reflux temperature for 4 hours. Once cooled to room temperature, 4- (3- (10-bromoanthracen-9-yl) phenyl) pyridine (9.0 g), Pd (dba) ₂ (0.38 g), tricyclohexylphosphine (0.37 g) , Potassium phosphate (12.0 g), t-butyl alcohol (1 ml) and 1,2,4-trimethylbenzene (50 ml) were added, and the mixture was further heated and stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, toluene was added, the solid in the solution was removed by suction filtration, and EDTA · 4Na aqueous solution was added to separate the solution. The solution was distilled off under reduced pressure and purified by silica gel column chromatography (developing solution: toluene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. The solvent was distilled off under reduced pressure, ethyl acetate was added to the resulting oil for precipitation, and the mixture was collected by suction filtration. Further, for color removal, activated carbon short column chromatography was performed to obtain a compound represented by the formula (1-19) (6.5 g).

The glass transition temperature (Tg) by DSC measurement was 141 ° C., and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.98 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.89 (m, 1H), 8.69 (t, 2H), 8.24 (d, 1H), 7.94 (td, 1H), 7.75 -7.90 (m, 8H), 7.60-7.70 (m, 4H), 7.56 (d, 2H), 7.49 (m, 1H), 7.43 (m, 1H), 7.36 (m, 2H), 7.22-7.29 (m, 3H).

<Synthesis Example of Anthracene Derivative Represented by Formula (1-24)>

4- (4-Bromophenyl) pyridine (5.5 g), bispinacolatodiboron (6.4 g), Pd (dppf) Cl ₂ (0.6 g), potassium acetate (6.9 g) and cyclopentyl methyl ether ( 50 ml) was heated and stirred at reflux temperature for 5 hours. Once cooled to room temperature, 4- (3- (10-bromoanthracen-9-yl) phenyl) pyridine (8.0 g), Pd (dba) ₂ (0.34 g), tricyclohexylphosphine (0.33 g) , Potassium phosphate (12.4 g), t-butyl alcohol (1 ml) and 1,2,4-trimethylbenzene (50 ml) were added, and the mixture was further heated and stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, chlorobenzene and an EDTA · 4Na aqueous solution were added and separated. The solution was distilled off under reduced pressure and purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. After the solvent was distilled off under reduced pressure, reprecipitation was further performed with chlorobenzene / methanol to obtain a compound (2.4 g) represented by the formula (1-24).

The glass transition temperature (Tg) determined by DSC measurement was 119 ° C., and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.95 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.76 (m, 2H), 8.68 (m, 2H), 7.91 (d, 2H), 7.87 (m, 1H), 7.80 (M, 1H), 7.72-7.79 (m, 5H), 7.70 (m, 2H), 7.58-7.65 (m, 5H), 7.38 (m, 4H).

<Synthesis Example of Anthracene Derivative Represented by Formula (1-36)>

3- (4-bromonaphthalen-1-yl) pyridine (3.0 g), bispinacolato diboron (3.2 g), Pd (dppf) Cl ₂ (0.3 g), potassium acetate (3.5 g) and A flask containing cyclopentyl methyl ether (20 ml) was heated and stirred at reflux temperature for 2 hours. Once cooled to room temperature, 4- (4- (10-bromoanthracen-9-yl) phenyl) pyridine (3.0 g), Pd (dba) ₂ (0.13 g), tricyclohexylphosphine (0.12 g) , Potassium phosphate (4.6 g), t-butyl alcohol (0.5 ml) and 1,2,4-trimethylbenzene (50 ml) were added, and the mixture was further heated and stirred at reflux temperature for 8 hours. After cooling the reaction solution to room temperature, the solid in the solution was collected by suction filtration, and washed with methanol, then water, and methanol. After washing, it was purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. After depressurizingly distilling a solvent, it reprecipitated with chlorobenzene / methanol and obtained the compound (1.3g) represented by Formula (1-36).

The glass transition temperature (Tg) determined by DSC measurement was 147 ° C., and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.95 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.97 (m, 1H), 8.77 (m, 3H), 8.03 (m, 1H), 8.00 (d, 1H), 7.94 (T, 2H), 7.80 (d, 2H), 7.66-7.74 (m, 6H), 7.54 (m, 3H), 7.48 (m, 1H), 7.38 ( m, 2H), 7.30 (m, 4H).

<Synthesis Example of Anthracene Derivative Represented by Formula (1-27)>

<Synthesis of 9- (6-methoxynaphthalen-2-yl) anthracene>
9-bromoanthracene (200.0 g), (6-methoxynaphthalen-2-yl) boronic acid (173.0 g), Pd (dba) ₂ (13.4 g), tricyclohexylphosphine (13.1 g), phosphoric acid A flask containing potassium (330.0 g), xylene (1000 ml), tetrahydrofuran (300 ml), isopropyl alcohol (300 ml) and water (300 ml) was heated and stirred at reflux temperature for 1.5 hours. The reaction solution was cooled to room temperature, water and ethyl acetate were added, and suction filtration was performed with a Kiriyama funnel with celite. The obtained filtrate was separated, and the organic layer was washed with an EDTA · 4Na aqueous solution and then with water. The solvent was distilled off under reduced pressure, and the resulting solid was washed with ethyl acetate. Further purification was performed by silica gel column chromatography (developing solution: chlorobenzene / heptane mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of chlorobenzene in the developing solution. After the target product was collected, the solvent was distilled off under reduced pressure to obtain 9- (6-methoxynaphthalen-2-yl) anthracene (227.0 g).

<Synthesis of 6- (anthracen-9-yl) naphthalen-2-ol>
A flask containing 9- (6-methoxynaphthalen-2-yl) anthracene (165.0 g), pyridine hydrochloride (285.0 g) and 1-methyl-2-pyrrolidone (NMP) (165 ml) at 175 ° C. Stir for 4 hours. After the reaction solution was cooled to room temperature, water was added to perform washing with heating, and a solid was collected by suction filtration. The obtained solid was heated and washed with methanol and then heptane to quantitatively obtain 6- (anthracen-9-yl) naphthalen-2-ol.

<Synthesis of 6- (anthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate>
A flask containing 6- (anthracen-9-yl) naphthalen-2-ol (217.0 g) and pyridine (500 ml) was cooled in an ice bath and trifluoromethanesulfonic anhydride (250.0 g) was added dropwise. . After completion of the dropwise addition, the mixture was stirred overnight at room temperature, and water and chlorobenzene were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography (chlorobenzene). Further, the solvent was distilled off under reduced pressure, and the resulting solid was washed with heptane by heating to obtain 6- (anthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate (206.0 g).

<Synthesis of 4- (6- (anthracen-9-yl) naphthalen-2-yl) pyridine>
6- (anthracen-9-yl) naphthalen-2-yl trifluoromethanesulfonate (27.0 g), 4-pyridineboronic acid (8.8 g), Pd (PPh ₃ ) ₄ (3.4 g), potassium phosphate A flask containing (25.0 g), xylene (150 ml), tetrahydrofuran (50 ml), isopropyl alcohol (50 ml) and water (50 ml) was heated and stirred at reflux temperature for 3.5 hours. After the reaction solution was cooled to room temperature, water and chlorobenzene were added to separate the solution, and the organic layer was washed with an EDTA · 4Na aqueous solution and then with water. The solvent was distilled off under reduced pressure, and the resulting solid was washed with ethyl acetate. Furthermore, it was purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. After separation of the desired product, the solvent was distilled off under reduced pressure, and the resulting solid was washed with warm heptane to give 4- (6- (anthracen-9-yl) naphthalen-2-yl) pyridine (19.0 g). Obtained.

<Synthesis of 4- (6- (10-bromoanthracen-9-yl) naphthalen-2-yl) pyridine>
Contains 4- (6- (anthracen-9-yl) naphthalen-2-yl) pyridine (19.0 g), N-bromosuccinimide (10.6 g), iodine (0.09 g) and tetrahydrofuran (300 ml). The flask was stirred at room temperature for 18 hours. Aqueous sodium sulfite was added and stirred vigorously, and then tetrahydrofuran was distilled off under reduced pressure. Next, the solid was collected by suction filtration and washed with warm water. Furthermore, it was purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. After the target product was collected, the solvent was distilled off under reduced pressure, and the precipitated crystals were collected by suction filtration to give 4- (6- (10-bromoanthracen-9-yl) naphthalen-2-yl) pyridine ( 17.1 g) was obtained.

<Synthesis of (10- (6- (pyridin-4-yl) naphthalen-2-yl) anthracen-9-yl) boronic acid>
A flask containing 4- (6- (10-bromoanthracen-9-yl) naphthalen-2-yl) pyridine (10.0 g) and tetrahydrofuran (200 ml) was cooled to −70 ° C. or lower with a dry ice / methanol bath. . A 1.6 M n-butyllithium hexane solution (15 ml) was added dropwise thereto, and trimethyl borate (3.6 ml) was added dropwise after stirring for 1 hour. After completion of the dropwise addition, the reaction solution was warmed to room temperature, 1M sulfuric acid was added, and the mixture was stirred for 1 hour. The solvent was distilled off under reduced pressure, and the precipitated solid was washed with methanol to give (10- (6- (pyridin-4-yl) naphthalen-2-yl) anthracen-9-yl) boronic acid (8.8 g). Obtained. The purity of (10- (6- (pyridin-4-yl) naphthalen-2-yl) anthracen-9-yl) boronic acid obtained here is not high, but without any further purification, Used in the next step.

<Synthesis of Compound Represented by Formula (1-27)>
(10- (6- (Pyridin-4-yl) naphthalen-2-yl) anthracen-9-yl) boronic acid (6.6 g), 4- (3-bromophenyl) pyridine (4.4 g), Pd ( dba) ₂ (0.27 g), tricyclohexylphosphine (0.26 g), potassium phosphate (9.9 g), 1,2,4-trimethylbenzene (50 ml), t-butyl alcohol (10 ml) and water (5 ml) ) Was stirred with heating at reflux temperature for 3 hours. After cooling the reaction solution to room temperature, water and toluene were added for liquid separation, and the organic layer was washed with EDTA · 4Na aqueous solution and then with water. After the solvent was distilled off under reduced pressure, the residue was purified by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. Furthermore, after refine | purifying with activated carbon column chromatography (developing liquid: toluene), the solvent was depressurizingly distilled, it recrystallized from chlorobenzene, and the compound (1.4g) represented by Formula (1-27) was obtained.

The glass transition temperature (Tg) as measured by DSC was 140 ° C., and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.93 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.76 (m, 2H), 8.69 (m, 2H), 8.31 (s, 1H), 8.18 (d, 1H), 8.05 (M, 2H), 7.87 (d, 2H), 7.82 (m, 1H), 7.71-7.80 (m, 7H), 7.69 (m, 1H), 7.61 ( m, 3H), 7.36 (m, 4H).

<Synthesis Example of Anthracene Derivative Represented by Formula (1-54)>

(10- (6- (Pyridin-4-yl) naphthalen-2-yl) anthracen-9-yl) boronic acid (2.0 g), 4- (4-bromophenyl) pyridine (1.3 g), Pd ( dba) ₂ (0.08 g), tricyclohexylphosphine (0.08 g), potassium phosphate (3.0 g), 1,2,4-trimethylbenzene (10 ml), t-butyl alcohol (2 ml) and water (2 ml) ) Was stirred with heating at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration, and the obtained solid was washed with EDTA · 4Na aqueous solution, water, and methanol in this order. Next, it was purified by activated alumina column chromatography (developing liquid: chlorobenzene), and further purified by activated carbon column chromatography (developing liquid: chlorobenzene). The solvent was distilled off under reduced pressure, and then recrystallized from chlorobenzene to obtain a compound (1.5 g) represented by the formula (1-54).

The glass transition temperature (Tg) by DSC measurement was not observed, and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.96 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.76 (m, 4H), 8.31 (s, 1H), 8.18 (d, 1H), 8.05 (m, 2H), 7.92 (D, 2H), 7.87 (dd, 1H), 7.63-7.80 (m, 11H), 7.37 (m, 4H).

<Synthesis Example of Anthracene Derivative Represented by Formula (1-42)>

<Synthesis of 9- (4-ethoxynaphthalen-1-yl) anthracene>
9-bromoanthracene (75.0 g), (4-ethoxynaphthalen-1-yl) boronic acid (78.0 g), Pd (dba) ₂ (5.0 g), tricyclohexylphosphine (4.9 g), phosphoric acid A flask containing potassium (124.0 g), 1,2,4-trimethylbenzene (400 ml) and t-butyl alcohol (40 ml) was heated and stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature, and the precipitated solid was collected by suction filtration, and the obtained solid was washed with EDTA · 4Na aqueous solution, water, and methanol in this order. The solid was dissolved in heated chlorobenzene and suction filtered with a Kiriyama funnel covered with silica gel. The solvent of the filtrate was distilled off under reduced pressure, and the obtained solid was washed with warm heptane to obtain 9- (4-ethoxynaphthalen-1-yl) anthracene (87.1 g).

<Synthesis of 4- (anthracen-9-yl) naphthalen-1-ol>
A flask containing 9- (4-ethoxynaphthalen-1-yl) anthracene (87.1 g), pyridine hydrochloride (289.0 g) and 1-methyl-2-pyrrolidone (NMP) (87 ml) at 175 ° C. Stir for 16 hours. The reaction solution was cooled to room temperature, and the precipitated solid was washed with warm water and collected by suction filtration. The obtained solid was heated and washed with methanol, dissolved in heated chlorobenzene, and subjected to suction filtration with a Kiriyama funnel covered with silica gel. An appropriate amount of the filtrate was distilled off under reduced pressure, and heptane was added for reprecipitation to obtain 4- (anthracen-9-yl) naphthalen-1-ol (74.3 g).

<Synthesis of 4- (anthracen-9-yl) naphthalen-1-yl trifluoromethanesulfonate>
A flask containing 4- (anthracen-9-yl) naphthalen-1-ol (74.0 g) and pyridine (500 ml) was cooled in an ice bath and trifluoromethanesulfonic anhydride (98.0 g) was added dropwise. . After completion of dropping, the mixture was stirred at room temperature for 1 hour, water was added, and the precipitated solid was collected by suction filtration. The obtained solid was washed with methanol, dissolved in toluene, and suction filtered with a Kiriyama funnel covered with silica gel. The filtrate was distilled off under reduced pressure, and then recrystallized from heptane to obtain 4- (anthracen-9-yl) naphthalen-1-yl trifluoromethanesulfonate (100.2 g).

<Synthesis of 4- (4- (anthracen-9-yl) naphthalen-1-yl) pyridine>
4- (anthracen-9-yl) naphthalen-1-yl trifluoromethanesulfonate (27.0 g), 4-pyridineboronic acid (8.8 g), Pd (PPh ₃ ) ₄ (1.4 g), potassium phosphate A flask containing (25.0 g), xylene (200 ml), isopropyl alcohol (50 ml) and water (25 ml) was heated and stirred at reflux temperature for 2 hours. After cooling the reaction solution to room temperature, water and toluene were added for liquid separation, and the organic layer was washed with EDTA · 4Na aqueous solution and then with water. The solvent was distilled off under reduced pressure, and the resulting solid was purified by activated alumina column chromatography (developing solution: toluene / ethyl acetate mixed solvent) to give 4- (4- (anthracen-9-yl) naphthalen-1-yl). Pyridine (19.9 g) was obtained. At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution.

<Synthesis of 4- (4- (10-bromoanthracen-9-yl) naphthalen-1-yl) pyridine>
Contains 4- (4- (anthracen-9-yl) naphthalen-1-yl) pyridine (19.9 g), N-bromosuccinimide (11.1 g), iodine (0.07 g) and tetrahydrofuran (300 ml). The flask was stirred at room temperature for 18 hours. A sodium sulfite aqueous solution was added and stirred vigorously, and then water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by activated alumina column chromatography (developing solution: toluene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. After fractionating the desired product, the solvent was distilled off under reduced pressure, and heptane was added to the resulting oily component for reprecipitation to give 4- (4- (10-bromoanthracen-9-yl) naphthalen-1-yl). Pyridine (22.2 g) was obtained.

<Synthesis of (10- (4- (pyridin-4-yl) naphthalen-1-yl) anthracen-9-yl) boronic acid>
A flask containing 4- (4- (10-bromoanthracen-9-yl) naphthalen-1-yl) pyridine (22.0 g) and tetrahydrofuran (200 ml) was cooled to −70 ° C. or lower with a dry ice / methanol bath. . A 1.6 M n-butyllithium hexane solution (33 ml) was added dropwise thereto, and after stirring for 1 hour, trimethyl borate (6.4 ml) was added dropwise. After completion of the dropwise addition, the reaction solution was warmed to room temperature, 1M sulfuric acid was added, and the mixture was stirred for 1 hour. The solvent was distilled off under reduced pressure, and the precipitated solid was washed with methanol to obtain (10- (4- (pyridin-4-yl) naphthalen-1-yl) anthracen-9-yl) boronic acid (18.0 g). It was. The purity of (10- (4- (pyridin-4-yl) naphthalen-1-yl) anthracen-9-yl) boronic acid obtained here is not high, but without further purification, Used in the next step.

<Synthesis of Compound Represented by Formula (1-42)>
(10- (4- (Pyridin-4-yl) naphthalen-1-yl) anthracen-9-yl) boronic acid (9.0 g), 4- (4-bromophenyl) pyridine (5.7 g), Pd ( dba) ₂ (0.35 g), tricyclohexylphosphine (0.34 g), potassium phosphate (8.7 g), 1,2,4-trimethylbenzene (100 ml), t-butyl alcohol (25 ml) and tetrahydrofuran (50 ml) ) Was stirred with heating at reflux temperature for 1 hour. After cooling the reaction solution to room temperature, water was added and the precipitated solid was obtained by suction filtration. The obtained solid was washed with an EDTA · 4Na aqueous solution and then with water. After further washing with methanol and then with ethyl acetate, purification was performed by activated alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the target product was eluted by gradually increasing the ratio of ethyl acetate in the developing solution. After evaporating the solvent in an appropriate amount under reduced pressure, ethyl acetate was added for reprecipitation to obtain a compound (6.3 g) represented by the formula (1-42).

The glass transition temperature (Tg) by DSC measurement was not observed, and the energy gap estimated by drawing a tangent to the absorption edge of the absorption spectrum was 2.96 eV.
Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 8.83 (d, 2H), 8.77 (d, 2H), 8.03 (d, 1H), 7.94 (t, 2H), 7.80 (D, 2H), 7.62-7.75 (m, 8H), 7.50 (d, 2H), 7.48 (m, 1H), 7.38 (t, 2H), 7.29 ( m, 4H).

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

The energy gap of each synthesized compound is shown in Table 1 below.

Regarding the method of measuring the energy gap, first, a thin film is prepared with a vapor deposition machine, the absorption curve of this thin film is measured using an ultraviolet-visible absorptiometer, and then a tangent line is placed at the rising edge on the short wavelength side of the absorption curve. By subtracting and substituting the obtained wavelength of the intersection into the following equation, the energy gap can be obtained.
Energy gap = 1240 / wavelength of intersection (nm)
For example, when the value obtained by drawing a tangent is 420 nm, the value of the energy gap at this time is calculated as follows.
Energy gap = 1240 ÷ 420 = 2.95 (eV)

On the other hand, the energy gap of each compound disclosed in JP2009-173642A (representative example of the compound of formula (1-6) below) is smaller than 2.90 eV. It can be seen that the compound of the present invention has an excellent exciton confinement effect.

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

The electroluminescent elements according to Examples 1 to 9 and Comparative Examples 1 to 4 were manufactured and driven at a constant current at a current density at which a driving start voltage (V) in a constant current driving test and a luminance of 2000 cd / m ² were obtained. At that time, the time (time) during which the luminance retained 90% or more of the initial luminance was measured. Hereinafter, examples and comparative examples will be described in detail.

Table 2 below shows the material configuration of each layer in the electroluminescent elements according to Examples 1 to 9 and Comparative Examples 1 to 4. In all cases, the cathode was composed of quinolinol lithium (Liq) / (magnesium + silver).

In Table 2, “HI” is N4, N4′-diphenyl-N4, N4′-bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4,4′-diamine. “NPD” is N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, and compound (A) is 9-phenyl-10- (4-phenylnaphthalen-1-yl) anthracene, the compound (B) is ^{N 5, N 5, N 9} , N 9 -7,7- hexaphenyl -7H- benzo [C] fluorene-5,9-diamine, compound (C) is 9,10-di ([2,2′-bipyridin] -5-yl) anthracene, compound (D) is 9,10-bis (4- (pyridin-4-yl) naphthalen-1-yl) anthracene, and compound (E) is 9 , 10-bis (4- (pyridin-4-yl) Eniru) anthracene compound (F) is 9,10-bis (4- (pyridin-2-yl) naphthalen-1-yl) anthracene, and "Liq" is 8-quinolinol lithium. The chemical structure is shown below.

<Example 1>
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 Vacuum Kiko 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 (B), molybdenum vapor deposition boat containing compound (1-6) of the present invention, molybdenum vapor deposition containing quinolinol lithium (Liq) A boat, a molybdenum boat containing magnesium, and a tungsten evaporation boat containing silver were installed.

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

  Thereafter, the vapor deposition boat containing quinolinol lithium (Liq) was heated and vapor-deposited at a vapor deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film pressure 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 from 0.1 nm to 10 nm to obtain an organic electroluminescent device.

When a direct current voltage was applied using the ITO electrode as the anode and the magnesium / silver electrode as the cathode, blue light emission with a wavelength of about 460 nm was obtained. In addition, a constant current driving test was performed at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving start voltage was 5.24 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 69 hours.

<Example 2>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (1-11). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the drive start voltage was 5.20 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 11 hours.

<Example 3>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (1-15). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving start voltage was 5.25 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 70 hours.

<Example 4>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (1-19). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the drive start voltage was 5.12 V, and the time for maintaining 90% (1800 cd / m ² ) or more of the initial brightness was 37 hours.

<Example 5>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (1-24). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving start voltage was 5.61 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 115 hours.

<Example 6>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (1-36). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving start voltage was 5.16 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 13 hours.

<Example 7>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (1-27). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving start voltage was 6.13 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 66 hours.

<Example 8>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (1-54). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving start voltage was 5.69 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 45 hours.

<Example 9>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (1-42). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the drive start voltage was 5.51 V, and the time for maintaining 90% (1800 cd / m ² ) or more of the initial brightness was 43 hours.

<Comparative Example 1>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (C). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the drive start voltage was 5.07 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 5 hours.

<Comparative example 2>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (D). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the driving start voltage was 5.17 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 7 hours.

<Comparative Example 3>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (E). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the drive start voltage was 5.17 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 8 hours.

<Comparative example 4>
An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-6) was changed to the compound (F). A constant current driving test was carried out using an ITO electrode as an anode and a magnesium / silver electrode as a cathode at a current density for obtaining an initial luminance of 2000 cd / m ² . As a result, the drive start voltage was 5.09 V, and the time for maintaining the luminance of 90% (1800 cd / m ² ) or more of the initial luminance was 10 hours.

Table 3 below summarizes the test results of the electroluminescent elements according to Examples 1 to 9 and Comparative Examples 1 to 4 described above.

  According to a preferred aspect of the present invention, it is possible to provide an organic electroluminescent element that improves the lifetime of the light emitting element and has an excellent balance with the driving voltage, a display device including the organic electroluminescent element, and a lighting device including the organic electroluminescent element. it can.

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 (20)

An anthracene derivative represented by the following formula (1).

In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, alkyl having 1 to 6 carbons, cycloalkyl having 3 to 6 carbons, or substituted Good aryl having 6 to 20 carbon atoms, and A and B are each independently a group represented by any of the following formulas (Py-1) to (Py-12), provided that A and B is not the same structure.

In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and A and B are each independently any one of the above formulas (Py-1) to (Py-12) The anthracene derivative according to claim 1, wherein A and B are not the same structure. In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and one of A and B is any one of the above formula (Py-1) to formula (Py-9) The other group is a group represented by any one of the above formulas (Py-1) to (Py-12), provided that A and B are not the same structure. Anthracene derivatives to be described. In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and one of A and B is any one of the above formula (Py-1) to formula (Py-3) The anthracene derivative according to claim 1, wherein the other is a group represented by any one of the above formulas (Py-4) to (Py-12). In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and one of A and B is any one of the above formula (Py-4) to formula (Py-9) The anthracene derivative according to claim 1, wherein the other is a group represented by any one of the formulas (Py-7) to (Py-12). The anthracene derivative according to claim 1, which is represented by the following formula (1-6).

The anthracene derivative according to claim 1, which is represented by the following formula (1-11).

The anthracene derivative according to claim 1, which is represented by the following formula (1-15).

The anthracene derivative according to claim 1, which is represented by the following formula (1-19).

The anthracene derivative according to claim 1, which is represented by the following formula (1-24).

The anthracene derivative according to claim 1, which is represented by the following formula (1-36).

The anthracene derivative according to claim 1, which is represented by the following formula (1-27).

The anthracene derivative according to claim 1, which is represented by the following formula (1-42).

The anthracene derivative according to claim 1, which is represented by the following formula (1-54).

  The electron transport material containing the anthracene derivative in any one of Claims 1-14.   An electron transport containing the electron transport material according to claim 15, disposed between a pair of electrodes composed of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, and the cathode and the light emitting layer. An organic electroluminescent device having a layer and / or an electron injection layer.   At least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of quinolinol-based metal complexes, pyridine derivatives, bipyridine derivatives, phenanthroline derivatives, borane derivatives, and benzimidazole derivatives. The organic electroluminescent element according to claim 16.   At least one of the electron transport layer and the electron injection layer may further include an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes, The organic electroluminescent element according to claim 16 or 17.   The display apparatus provided with the organic electroluminescent element in any one of Claims 16-18.   The illuminating device provided with the organic electroluminescent element in any one of Claims 16-18.

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