KR20120041110A - Anthracene derivative and organic electroluminescence element using the same - Google Patents

Abstract

PURPOSE: An anthracene derivative and an organic electroluminescence device using the same are provided to form an electron transport layer and/or electron injection layer. CONSTITUTION: An anthracene derivative is denoted by chemical formula 1. An electron transport material contains the anthracene derivative of chemical formula 1. An organic electroluminescence device comprises a pair of electrodes; a light emitting layer between the pair of electrodes; and an electron transport layer and/or electron injection layer. At least one among electron transport layer and electron injection layer contains quinnolinole-based metal complex, pyridine derivative, non-pyridine derivative, boran derivative or benzoimidazole derivative.

Description

Anthracene derivatives and organic electroluminescent devices using the same {ANTHRACENE DERIVATIVE AND ORGANIC ELECTROLUMINESCENCE ELEMENT USING THE SAME}

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

Background Art Conventionally, display apparatuses using light emitting elements that emit electroluminescence have been studied in various ways because they can be reduced in power and thinned, and organic electroluminescent elements made of organic materials have been actively studied because of their light weight and size. In particular, the development of organic materials having luminescent properties, including blue, which is one of the three primary colors of light, and the development of organic materials having charge transport ability (possibly to be semiconductors or superconductors), such as holes and electrons, are described as Regardless of their molecular weight, they have been actively studied to date.

For example, an organic electroluminescent device using a compound in which a pyridylphenyl group is substituted in the central skeleton of anthracene has also been reported (Japanese Unexamined Patent Publication No. 2009-173642 (Patent Document 1) and Japanese Unexamined Patent Publication No. 2005-170911 ( Patent document 2)). Moreover, the organic electroluminescent element using the compound by which the bipyridyl group was substituted by the center skeleton of anthracene is also reported (Japanese Unexamined-Japanese-Patent No. 2007/086552 (patent document 3)).

(Patent Document 1) Japanese Unexamined Patent Publication No. 2009-173642

(Patent Document 2) Japanese Unexamined Patent Publication No. 2005-170911

(Patent Document 3) Japanese Patent Publication No. 2007/086552

As described above, there are several known light emitting device materials for compounds in which the central skeleton of anthracene is substituted with a pyridylphenyl group or a bipyridyl group, and these known materials are known to have a pyridylphenyl group or a ratio in the anthracene skeleton for improving heat resistance In addition to the substitution position where the pyridyl group is substituted, it has a substituent. As a result, the confinement effect of the excitons to the light emitting layer, which is generally required for the electron transporting material by decreasing the energy gap by the amount of the substituent, is not sufficient in the blue device. Therefore, the electron transporting material is not particularly preferable for improving the characteristics of the blue light emitting device that is desired. The energy gap is wider, and development of an excellent electron transporting material is desired.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, in order to obtain the organic electroluminescent element especially which the characteristic in a blue element was improved, it provided with the organic layer containing an anthracene derivative represented by following formula (1) as an electron carrying material. It was found that it is effective to complete the present invention. This invention is comprised by the following each term.

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

[Chemical Formula 12]

In said formula (1), R <^1> , R <^2> , R <^3> and R <^4> are respectively independently hydrogen, C1-C? 6 alkyl, 3? 6 cycloalkyl or C 6? 20 is aryl, and A and B are each independently the following formula (Py-1)? It is group represented by either of formula (Py-12), but A and B are not the same structure.

[Formula 13]

[2] In the formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and A and B are each independently the formula (Py-1)? An anthracene derivative as described in said [1] which is group represented by either of formula (Py-12), and A and B are not the same structure.

[3] In the formula (1), R ¹ , R ² , R ³ and R ⁴ are hydrogen, and one of A and B is the formula (Py-1)? Is a group represented by any of formula (Py-9), and the other is a said formula (Py-1)? An anthracene derivative as described in said [1] which is group represented by either of formula (Py-12), and A and B are not the same structure.

[4] In said Formula (1), R <^1> , R <^2> , R <^3> and R <^4> are hydrogen, and one of A and B is said Formula (Py-1)? Is a group represented by any of formula (Py-3), and the other is a said formula (Py-4)? The anthracene derivative as described in said [1] which is group represented by either of formula (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 the formula (Py-4)? Is a group represented by any of formula (Py-9), and the other is a said formula (Py-7)? The anthracene derivative as described in said [1] which is group represented by either of formula (Py-12).

[6] The anthracene derivative according to the above [1], represented by the following Formula (1-6).

[Formula 14]

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

[Formula 15]

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

[Formula 16]

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

[Formula 17]

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

[Formula 18]

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

[Formula 19]

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

[Formula 20]

[13] The anthracene derivative according to the above [1], represented by the following Formula (1-42).

[Formula 21]

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

[Formula 22]

[15] The above [1]? The electron transport material containing the anthracene derivative as described in any one of [14].

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

[17] At least one of the electron transport layer and the electron injection layer may be further selected from a 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 as described in said [16] containing a.

[18] At least one of the electron transporting layer and the electron injecting layer may further include an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, and a rare earth metal. The organic electric field described in [15] or [17] containing at least one selected from the group consisting of oxides, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals. Light emitting element.

[19] The above [16]? The display apparatus provided with the organic electroluminescent element in any one of [18].

[20] The above [16]? The illuminating device provided with the organic electroluminescent element in any one of [18].

 According to a preferred embodiment of the present invention, by using an anthracene derivative having a low crystallinity and capable of forming a stable amorphous film, a stable electron transport layer and / or an electron injection layer can be formed, and thus a stable light emitting device 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 on the light emitting layer, which is generally required for electron transport materials, is improved, and in particular, the characteristics of a blue light emitting device. The electron transport material suitable for improvement can be provided. In addition, since a blue light emitting element having an element lifetime comparable to a red or green light emitting element can be manufactured, a high performance display device such as a full color display can be obtained.

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

1. Compound represented by formula (1)

The anthracene derivative of this invention is demonstrated in detail. The anthracene derivative of this invention is a compound represented by said Formula (1).

R <^1> , R <^2> , R <^3> and R <^4> (henceforth "R <^1> -R < ⁴ >>) of Formula (1) are respectively independently hydrogen, C1-C? 6 alkyl, 3? 6 cycloalkyl or C 6? It can select from 20 aryl suitably.

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

R ¹ of Formula (1)? Carbon number in R ⁴ ? Specific examples of the cycloalkyl of 6 include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl or dimethylcyclohexyl.

R ¹ of Formula (1)? "R 6 -C6 carbon number which may be substituted" in R <^4> About 20 aryl "6-? Aryl of 20 &quot; 16 aryl is preferred. More preferably, it is C6? 12 is aryl.

"6 carbon number? 20 aryl ", which is 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, condensed bicyclic aryl (1-, 2-) naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'- 1, m-terphenyl-5'-yl, o-terphenyl-3'-yl, o-terphenyl-4'-yl, p-terphenyl-2'-yl, m-terphenyl-2-yl , m-terphenyl-3-yl, m-terphenyl-4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terphenyl-4-yl, p-terphenyl -2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), anthracene- (1-, 2-, 9-) yl, condensed tricyclic aryl, acenaphthylene- (1 -, 3-, 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, penalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, triphenylene- (1-, 2-) yl, condensed tetracyclic aryl, pyrene- (1-, 2-, 4-) yl, tetracene -(1-, 2-, 5-) yl, condensed 5-ring aryl Perylene-yl, and the like (1, 2, 3).

Preferable "carbon number 6? 20 aryl "is phenyl, biphenylyl, terphenylyl or naphthyl, more preferably phenyl, biphenylyl, 1-naphthyl, 2-naphthyl or m-terphenyl-5'-yl. , More preferably, phenyl, biphenylyl, 1-naphthyl or 2-naphthyl, most preferably phenyl.

R ¹ of Formula (1)? Of R ⁴ "C 6? Alkyl is mentioned as a "substituent" which may be substituted by "aryl of 20", and R ¹ ? The same thing as what was described in the column of the "alkyl" in R <^4> is mentioned.

R ¹ ? Of R ⁴ "C 6? As the "substituent" which may be substituted with "20 aryl", specifically, 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. The number of substituents is a number which can be substituted maximum, for example, Preferably it is 1? Three, more preferably 1? Two, more preferably one. However, unsubstituted is most preferred.

R ¹ ? As specific examples of R ⁴ , the following groups may be mentioned. In addition, R in the structural formula is R ¹ ? The same thing as what was described in the column of the "alkyl" in R <^4> is mentioned.

(23)

[Formula 24]

As described later, the anthracene derivative according to the present invention has the asymmetric molecular structure in which A and B in the formula (1) do not have the same structure, so that the order of molecules is arranged when forming an organic layer in an organic EL device. It is a material that is expected to have an effect that disrupts the crystallization and prevents crystallization. Therefore, R ¹ ? Although all of R <^4> may be the same or different, considering that it can manufacture by a simple method in addition to this effect, R <^1> ? Compounds in which R ⁴ is hydrogen, methyl, ethyl, t-butyl, phenyl, in particular R ¹ ? Compounds in which R ⁴ is hydrogen or methyl are preferable, and furthermore, considering that the energy gap is wider, R ¹ ? Preference is given to compounds in which all of R ⁴ are hydrogen.

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

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

As a combination of A and B, either of A and B is a formula (Py-1)? The case where it is the group chosen from a formula (Py-6) is preferable. This is the formula (Py-1)? Among the groups represented by the formula (Py-12), in particular, the formula (Py-1)? This is because the group represented by the formula (Py-6) has a structure capable of more disrupting the symmetry of the molecular structure when substituted with an anthracene derivative.

Moreover, especially, either of A and B is a formula (Py-1)? In the case where the formula (Py-3) is selected, the other is the formula (Py-4)? The case where it is group chosen from a formula (Py-12) is preferable. This is because, as described above, A and B are preferably selected from different groups to have a molecular structure having greater asymmetry. Moreover, in one aspect of the present invention, the other formula (Py-4)? The group chosen from Formula (Py-9) is mentioned, In another aspect, the other is Formula (Py-7)? The case where it is group chosen from a formula (Py-9) is mentioned.

Moreover, in particular, either of A and B is a formula (Py-4)? When the formula (Py-6) is selected, the other is the formula (Py-1)? Expression (Py-3), Expression (Py-7)? The case where it is group chosen from a formula (Py-12) is preferable. This is because, as described above, A and B are preferably selected from different groups to have a molecular structure having greater asymmetry. Moreover, in one aspect of this invention, the other is a formula (Py-7)? The case where it is group chosen from a formula (Py-9) is mentioned.

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

In one embodiment of the present invention, both A and B are formulas (Py-4)? It is not selected from the group of formula (Py-6). Moreover, in one aspect of the present invention, A and B are both formulas (Py-10)? It is not selected from the group of formula (Py-12).

[Formula 25]

As a specific example of the anthracene derivative represented by said formula (1), it is a following formula (1-1)? Anthracene derivative represented by a formula (1-66) is mentioned. Among these, following formula (1-1)? The anthracene derivative represented by Formula (1-54) is preferable. More preferably, it is following formula (1-1)? It is an anthracene derivative represented by Formula (1-45).

[Formula 26]

[Formula 27]

[Formula 28]

[Formula 29]

(30)

2. Manufacturing method of anthracene derivative represented by formula (1)

Next, the manufacturing method of the anthracene derivative of this invention is demonstrated. The anthracene derivative of the present invention is basically a known synthesis method using a known compound, for example, a Suzuki coupling reaction or a Negishi coupling reaction (for example, "Metal-Catalyzed Cross-Coupling Reactions-Second, Completely"). Revised and Enlarged Edition, etc.). Moreover, it can synthesize | combine also by combining both reactions. The scheme which synthesize | combines the anthracene derivative represented by Formula (1) by a Suzuki coupling reaction or a Negishi coupling reaction is illustrated below.

When producing the anthracene derivative of the present invention, (1) a method of synthesizing a group in which a terminal group and an intermediate group are bonded to each other, and (2) a method of bonding an anthracene to a 9, 10 position of anthracene, And a terminal group bonded to the intermediate group. In addition, the coupling | bonding of a halogen group or a trifluoromethanesulfonate functional group, a zinc chloride complex, or boronic acid (boronic acid ester) is basically used for the coupling | bonding of the intermediate group and the terminal group, or anthracene and an intermediate group in these methods. Ring reactions can be used.

(1) How to combine "terminal-middle" group in 9, 10 position of anthracene

<"Terminal-middle" group: having a reactive substituent Pyridylphenyl  Synthesis>

First, the zinc chloride complex of pyridine is synthesize | combined according to following Reaction formula (1), Next, the zinc chloride complex of pyridine and m-dibromobenzene are made to react according to following Reaction formula (2), and it is 2- (3-bromophenyl Pyridine can be synthesized. Further, "ZnCl _2? TMEDA" in the reaction formula (1) is tetramethylethylenediamine complex of zinc chloride. In "RLi" and "RMgX" in Reaction formula (1), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? It is a branched alkyl group of 4, and X is halogen.

[Formula 31]

Here, the synthesis method using 2-bromopyridine as a raw material of an end group was illustrated, It respond | corresponds by using 3-bromopyridine or 4-bromopyridine as raw material, and using iodide instead of bromide, respectively. A target can be obtained.

Here, the synthesis method using m-dibromobenzene as the raw material of the intermediate group is illustrated, but by using p-dibromobenzene, 1,4-dibromonanaphthalene and 2,6-dibromonaphthalene as raw materials In addition, it is also possible to use not dibromo but dichloro, diiodine, bis (trifluoromethanesulfonate) or mixtures thereof (for example, 1-bromo-3-iodobenzene). You can get the object. In addition, 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 with boron tribromide or pyridine hydrochloride, followed by trifluoromethanesulfonic acid ester. The object can also be obtained through anger.

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

<Method for converting reactive substituent to boronic acid / boronic acid ester>

According to the following Reaction Scheme (3), 2- (3-bromophenyl) pyridine is lithiated using an organolithium reagent or a Grignard reagent using magnesium or an organic magnesium reagent, trimethyl borate and triethyl borate Or (3- (pyridin-2-yl) phenyl) boronic acid ester can be synthesized by reacting with triisopropyl borate or the like. In addition, according to the following reaction formula (4), (3- (pyridin-2-yl) phenyl) boronic acid can be synthesized by hydrolyzing the (3- (pyridin-2-yl) phenyl) boronic acid ester. . In "RLi" and "RMgX" in Reaction formula (3), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? It is a branched alkyl group of 4, and X is halogen.

[Formula 32]

Moreover, according to following Reaction formula (5), 2- (3-bromophenyl) pyridine is lithiated using an organolithium reagent, or it is made into a Grignard reagent using magnesium or an organic magnesium reagent, and bis (pinacola) Other 3- (pyridin-2-yl) phenyl) boronic acid esters can be synthesized by reacting with earth) diborone or 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-dioxabo The same 2,2'-bipyridine boronic acid ester can be synthesize | combined by carrying out coupling reaction of a rollan using a palladium catalyst and a base. In "RLi" and "RMgX" in Reaction formula (5), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? It is a branched alkyl group of 4, and X is halogen.

[Formula 33]

In addition, in said reaction formula (3), (5), or (6), even if another positional isomer is used instead of 2- (3-bromophenyl) pyridine, the corresponding boronic acid / boronic acid ester can be synthesize | combined. In addition, instead of bromide such as 2- (3-bromophenyl) pyridine, chloride, iodide or trifluoromethanesulfonate can be used in the same manner.

<Synthesis of central skeleton anthracene having reactive substituents>

<9,10-dibromoanthracene>

As shown in following Reaction Formula (7), 9,10-dibromoanthracene can be obtained by brominating anthracene using a suitable brominating agent. Suitable brominating agents include bromine or N-brominated succinimide (NBS).

[Formula 34]

In addition, when an anthracene derivative having a substituent (alkyl, cycloalkyl, aryl, etc.) at the 2-position is desired, an anthracene at 2-position is substituted with a halogen or a triflate and boronic acid (or boronic acid ester of a group corresponding to the substituent) By Suzuki coupling), anthracene derivatives having a substituent at the 2-position can be synthesized. Moreover, as another method, the synthesis | combining method by Negishi coupling of the anthracene substituted by the 2-position into halogen or a trilate, and the zinc complex of the group corresponding to the said substituent is mentioned. Moreover, the synthesis | combining method by Suzuki coupling of the group corresponding to the said substituent substituted by 2-anthracene boronic acid (or boronic acid ester) and halogen or triflate, Furthermore, substitution by 2-anthracene zinc complex, halogen or triflate The synthesis method by Negishi coupling of the group corresponding to the said substituted group is also mentioned. In addition, the anthracene derivative having a substituent in addition to the 2-position can be synthesized in the same manner by using a raw material in which the position of the halogen, triflate, boronic acid (or boronic acid ester) or zinc complex substituted in the anthracene is a desired position. have.

<9,10-dianthracene zinc complex>

As shown in the following Reaction Formula (8), 9,10-dibromoanthracene is lithiated using an organolithium reagent, or a Grignard reagent is used with magnesium or an organic magnesium reagent, and zinc chloride or zinc chloride tetra By reacting with a methylethylenediamine complex (ZnCl ₂ -TMEDA), a 9,10-dianthracene zinc complex can be synthesized. In Reaction formula (8), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? 4 is a branched alkyl group. In addition, instead of bromide such as 9,10-dibromoanthracene, chloride or iodide can be used in the same manner.

[Formula 35]

<9,10-anthracenediboronic acid (or boronic acid ester)>

As shown in the following reaction formula (9), 9,10-dibromoanthracene is lithiated using an organolithium reagent, or a Grignard reagent is used with magnesium or an organic magnesium reagent, trimethyl borate and triethyl borate Alternatively, by reacting with triisopropyl borate or the like, 9,10-anthracenediboronic acid ester can be synthesized. Moreover, 9,10- anthracene diboronic acid can be synthesize | combined by hydrolyzing the 9,10- anthracene diboronic acid ester in following Reaction formula (10). In Reaction formula (9), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? 4 is a branched alkyl group.

[Formula 36]

Moreover, as shown in following Reaction formula (11), 9,10- dibromo anthracene is lithiated using an organolithium reagent, or it is made into a Grignard reagent using magnesium or an organic magnesium reagent, and bis (pina-cola) Another 9,10-anthracenediboronic acid ester can be synthesize | combined by reacting with th) diborone or 4,4,5,5-tetramethyl-1,3,2-dioxaborolane. In addition, as shown in the following scheme (12), 9,10-dibromoanthracene and bis (pinacolato) diboron or 4,4,5,5-tetramethyl-1,3,2-dioxabo The same 9,10-anthracene diboronic acid ester can be synthesize | combined by making a coupling reaction of a rollan using a palladium catalyst and a base. In Reaction formula (11), although R represents a linear or branched alkyl group, Preferably it is C1-C? Straight chain or carbon number of 4? 4 is a branched alkyl group.

[Formula 37]

In addition, in the said reaction formula (9), (11) or (12), it can synthesize | combine similarly even if it uses chloride, iodide, or triflate instead of bromide like 9,10- dibromoanthracene. .

<Method for combining anthracene having a substituent and a "terminal-middle" group>

As mentioned above, about the "terminal-middle" group, the bromomer of pyridylphenyl (reaction formula (1)-(2)), boronic acid, a boronic acid ester (reaction formula (3)-(6)) are synthesize | combined. About the anthracene having a substituent, an anthracene bromomer (Scheme (7)), a zinc chloride complex (Scheme (8)), boronic acid, a boronic acid ester (Scheme (9)-(12)) can be synthesized. Therefore, the anthracene derivative of this invention can be synthesize | combined by combining the "terminal-middle" group and anthracene with reference to the coupling reaction used by the description so far.

In this final coupling reaction, in order to make A and B of the anthracene derivative represented by Formula (1) into a different structure, first, an anthracene having a substituent was reacted with a compound of a "terminal-middle" group equivalent to 1 mole. Thereafter, this intermediate is reacted with a compound of a "terminal-middle" group different from the first (ie, reacted in two steps).

(2) at 9, 10 position Mid-term  With combined anthracene Terminal group  How to combine

Also about this method, with reference to the various coupling reactions mentioned above, the intermediate | middle group may be couple | bonded with the 9, 10 position of anthracene, and what is necessary is just to couple an end group to this intermediate group. At this time, in order to make A and B of the anthracene derivative represented by Formula (1) into a different structure, in the binding step of the intermediate group to anthracene, a different intermediate group is bonded by two-step reaction, or the end group is bonded to the intermediate group. The desired anthracene derivative can be synthesized by binding different end groups in two stage reactions.

<About Reagents Used in 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) 2 palladium (0), tris ( Dibenzylideneacetone) 2 palladium (0) chloroform complex, bis (dibenzylideneacetone) palladium (0), bis (trit-butylphosphino) palladium (0), or (1,1'-bis (diphenyl) Phosphino) ferrocene) dichloropalladium (II) is mentioned.

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

Specific examples of the base used in the reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, potassium triphosphate, Or potassium fluoride.

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

3. Organic Field  Light emitting element

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

<Structure of Organic Electroluminescent Element>

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

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

It is not necessary that all of the above layers be present, and the minimum structural unit is composed of an anode 102, a light emitting layer 105, an electron transport layer 106 and / or an electron injection layer 107, and a cathode 108. The hole injection layer 103 and the hole transport layer 104 are optionally formed layers. Moreover, each said layer may consist of a single layer, and may consist of multiple layers, respectively.

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

<Substrate in Organic Electroluminescent Element>

The substrate 101 serves as a support for the organic electroluminescent element 100, and usually quartz, glass, metal, plastic, or the like is used. The board | substrate 101 is formed in plate shape, a film form, or a sheet form according to the objective, For example, a glass plate, a metal plate, metal foil, a plastic film, a plastic sheet, etc. are used. Especially, the plate made from transparent synthetic resins, such as a glass plate and polyester, a polymethacrylate, a polycarbonate, and a polysulfone, is preferable. Soda-lime glass, an alkali free glass, etc. are used as it is a glass substrate, and since thickness should just be sufficient thickness to maintain mechanical strength, for example, what is necessary is just 0.2 mm or more. As an upper limit of thickness, it is 2 mm or less, for example, Preferably it is 1 mm or less. For the material of the glass, therefore less good eluted ions from the glass side the alkali-free glass of shifting preferable, soda subjected to barrier coating of SiO _2, such as lime glass, because also commercially available it can be used. Moreover, in order to improve gas barrier property, the board | substrate 101 may form a gas barrier film | membrane, such as a dense silicon oxide film, at least in single side | surface, Especially the board | substrate 101 which consists of a synthetic resin plate, film, or sheet with low gas barrier property is carried out. In using, it is preferable to form a gas barrier film.

<Anode in organic electroluminescent element>

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

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

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

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

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

As the hole injection / transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes given an electric field, high hole injection efficiency, and transporting the injected holes efficiently. For this purpose, it is preferable that the ionization potential is small, the hole mobility is large, the stability is further excellent, and the impurity which becomes a trap is a substance which is hard to generate | occur | produce at the time of manufacture and use.

As a material for forming the hole injection layer 103 and the hole transport layer 104, a hole injection layer of a compound, a p-type semiconductor, and an organic electroluminescent element conventionally used as a charge transport material for holes in a photoconductive material And any known ones used in the hole transport layer. Specific examples thereof include biscarbazole derivatives such as carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, and the like), bis (N-arylcarbazole) or bis (N-alkylcarbazole), and triarylamine derivatives ( Polymer having 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'-diphenyl-N, N'-di (3) having an aromatic tertiary amino group in the main chain or in the side chain -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 Triphenylamine derivatives such as -1,1'-diamine, 4,4 ', 4'-tris (3-methylphenyl (phenyl) amino) triphenylamine, and starburst amine derivatives, stilbene derivatives and phthalocyanine derivatives Metals, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives, oxadiazole induction And heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonate, styrene derivatives, polyvinylcarbazole and polysilane having the above monomers in the side chain are preferable. It will not specifically limit, if it is a compound which can form, inject | pours a hole from an anode, and can transport a hole.

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

<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 the electrodes provided with the electric field. The material for forming the light emitting layer 105 may be a compound (light emitting compound) that is excited by light recombination of holes and electrons to emit light, and can form a stable thin film shape, and also has strong light emission in a solid state (fluorescence and / Or phosphorescent) efficiency.

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

The usage-amount of a host material changes with kinds of host material, and what is necessary is just to determine according to the characteristic of the host material. The criterion of the amount of use of the host material is preferably 50? 99.999 weight%, More preferably, it is 80? 99.95 weight%, More preferably, it is 90? 99.9% by weight.

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

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

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

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

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

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

Again, green? Examples of the yellow dopant material include naphthacene such as coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridon derivatives, quinacridone derivatives, and rubrene. Derivatives, and the like. The compound which introduce | transduced the substituent which enables long wavelengths, such as an aryl group, a heteroaryl group, an aryl vinyl group, an amino group, and a cyano group, is mentioned as a preferable example to the compound illustrated by the cyan dopant material.

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

In addition, it can select suitably from a compound etc. which were described in the chemical industry June 2004 issue page 13, the reference literature etc. which were illustrated to it, etc. as a dopant.

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

Examples of the perylene derivatives include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene and 3,10-diphenyl Perylene, 3,4-diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) -8,11-di (t-butyl) perylene, 3- (9'-anthryl) -8,11-di (t-butyl) perylene, 3,3'-bis (8,11-di ( t-butyl) perylenyl), and the like.

Japanese Unexamined Patent Publication No. Hei 11-97178, Japanese Unexamined Patent Publication No. 2000-133457, Japanese Unexamined Patent Publication No. 2000-26324, Japanese Unexamined Patent Publication No. 2001-267079, Japanese Unexamined Patent Publication No. 2001-267078, You may use the perylene derivative as described in Unexamined-Japanese-Patent No. 2001-267076, Unexamined-Japanese-Patent No. 2000-34234, Unexamined-Japanese-Patent No. 2001-267075, Unexamined-Japanese-Patent No. 2001-217077, etc.

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

Moreover, you may use the borane derivative as described in international publication 2000/40586 pamphlet etc.

As the amine-containing styryl derivative, for example, N, N, N ', N'-tetra (4-biphenylyl) -4,4'-diaminostilbene, N, N, N', N ' Tetra (1-naphthyl) -4,4'-diaminostilbene, N, N, N ', N'-tetra (2-naphthyl) -4,4'-diaminostilbene, N, N '-Di (2-naphthyl) -N, N'-diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) -N, N'-diphenyl-4 , 4'-diaminostilbene, 4,4'-bis [4′-bis (diphenylamino) styryl] -biphenyl, 1,4-bis [4'-bis (diphenylamino) styryl] -Benzene, 2,7-bis [4'-bis (diphenylamino) styryl] -9,9-dimethylfluorene, 4,4'-bis (9-ethyl-3-carbazovinylene) -ratio Phenyl, 4,4'-bis (9-phenyl-3-carbazovinylene) -biphenyl, etc. are mentioned. Moreover, you may use the amine containing styryl derivative of Unexamined-Japanese-Patent No. 2003-347056, Unexamined-Japanese-Patent No. 2001-307884, etc. can also be used.

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

Moreover, you may use the aromatic amine derivative as described in Unexamined-Japanese-Patent No. 2006-156888.

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

Moreover, you may use the coumarin derivative as described in Unexamined-Japanese-Patent No. 2004-43646, Unexamined-Japanese-Patent No. 2001-76876, 6-298758, etc.

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

[Formula 38]

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

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

[Formula 39]

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

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

[Formula 40]

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

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

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

The electron injection-transport layer is a layer in which electrons are injected from the cathode and is responsible for transporting electrons. The electron injection efficiency is high, and it is preferable to transport the injected electrons efficiently. For this purpose, it is preferable that the electron affinity is large, the electron mobility is large, further excellent stability, and the impurity which becomes a trap hardly arises at the time of manufacture and use. However, in view of the balance between the transport of holes and electrons, in the case of mainly playing a role of effectively preventing the holes from the anode from flowing back to the cathode side without recombination, the luminous efficiency is improved even if the electron transport capacity is not very high. The effect of making it have the same effect as a material with high electron transport ability. Therefore, the electron injection / transport layer in the present embodiment may also include a function of a layer capable of effectively preventing the movement of holes.

As a material (electron transport material) which forms the electron carrying layer 106 or the electron injection layer 107, the compound represented by said Formula (1) can be used. Especially, said formula (1-1)? The anthracene derivative represented by Formula (1-66) is preferable.

Content of the anthracene derivative represented by the said Formula (1) in the electron carrying layer 106 or the electron injection layer 107 changes with kinds of derivatives, and may be determined according to the characteristic of the derivative. The reference for the content of the anthracene derivative represented by the formula (1) is preferably 1 to the whole of the electron transport layer material (or the electron injection layer material). 100 weight%, More preferably, it is 10? 100 weight%, More preferably, it is 50? 100 weight%, Especially preferably, it is 80? 100 wt%. When not using the anthracene derivative represented by said formula (1) alone (100 weight%), what is necessary is just to mix the other material mentioned in detail below.

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

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

Moreover, as a specific example of another electron transfer compound, a pyridine derivative, a naphthalene derivative, an anthracene derivative, a phenanthroline derivative, a perinone derivative, a coumarin derivative, a naphthalimide derivative, an anthraquinone derivative, a diphenoquinone derivative, a diphenylquinone Derivatives, perylene derivatives, oxadiazole derivatives (1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene, etc.), thiophene derivatives, triazole derivatives (N- Naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of auxin derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazoles Compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis (benzo [h] quinolin-2-yl) -9,9 ' -Spirobifluorene, etc.), imidazopyridine derivative, borane derivative, benzimidazole derivative (t Oligopyridine derivatives such as s (N-phenylbenzoimidazol-2-yl) benzene), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives, terpyridine, bipyridine derivatives and terpyridine derivatives (1,3- Bis (4 '-(2,2': 6 ', 2'-terpyridinyl)) benzene, etc.), naphthyridine derivatives (bis (1-naphthyl) -4- (1,8-naphthyridine-) 2-yl) phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, inoxide derivatives, bisstyryl derivatives, and the like.

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

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

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

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

[Formula 41]

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

Specific examples of the quinolinol-based metal complexes include 8-quinolinolithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl- 8-quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl -8-quinolinolato) aluminum, bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolate) aluminum , Bis (2-methyl-8-quinolinolato) (3-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (4-methylphenolate) aluminum, bis (2-methyl -8-quinolinolato) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2-methyl-8-quinolinola Earth) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) alu Aluminum, bis (2-methyl-8-quinolinolato) (2,6-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, Bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-di-t-butylphenolate) Aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-triphenylphenol Aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,5, 6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (1-naphthorate) aluminum, bis (2-methyl-8-quinolinolato) (2-naphthorate Aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolate) aluminum , Bis (2,4-di Methyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2,4- Dimethyl-8-quinolinolato) (3,5-di-t-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) aluminum-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-trifluorome Am-8-quinolinyl Sat), and the like of aluminum, bis (10-hydroxybenzo [h] quinoline) beryllium.

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

[Formula 42]

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

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

[Formula 43]

Specific examples of the pyridine derivatives include 2,5-bis (2,2'-bipyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilol, 2,5-bis (2,2 '-Bipyridin-6-yl) -1,1-dimethyl-3,4-dimethylsilol, 2,5-bis (2,2'-bipyridin-5-yl) -1,1-dimethyl- 3,4-diphenylsilol, 2,5-bis (2,2'-bipyridin-5-yl) -1,1-dimethyl-3,4-dimethylsilol, 9,10-di (2, 2'-bipyridin-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'-bipyridin-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'-BP Din-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 '' quaterpyridine and the like.

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

[Formula 44]

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

Specific examples of the phenanthroline derivatives include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10- Di (1,10-phenanthroline-2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5-tri (1,10-phenanthrole Lin-5-yl) benzene, 9,9'-difluoro-bis (1,10-phenanthroline-5-yl), vasocuproin or 1,3-bis (2-phenyl-1,10- Phenanthroline-9-yl) benzene and the like.

In particular, the case where a phenanthroline derivative is used for an electron carrying layer and an electron injection layer is demonstrated. In order to obtain stable light emission over a long period of time, a material having excellent thermal stability and thin film formation property is desired, and among the phenanthroline derivatives, the substituents themselves have a three-dimensional structure or with a phenanthroline skeleton or with adjacent substituents. It is preferable to have a three-dimensional three-dimensional structure or to connect a plurality of phenanthroline skeletons by steric repulsion. Moreover, when connecting several phenanthroline frame | skeleton, the compound which contains the conjugated bond, substituted or unsubstituted aromatic hydrocarbon, and substituted or unsubstituted aromatic heterocyclic ring in a connection unit is more preferable.

Borane derivatives are compounds represented by the following general formula (E-4), and are disclosed in JP 2007-27587 A in detail.

[Formula 45]

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

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

[Formula 46]

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

[Formula 47]

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

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

(48)

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

[Formula 49]

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

Among the compounds represented by the general formula (E-4), a compound represented by the following general formula (E-4-3), and also the following general formula (E-4-3-1) or (E-4-3-2) The compound represented by is preferable.

[Formula 50]

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

[Formula 51]

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

Benzimidazole derivatives are compounds represented by the following general formula (E-5).

(52)

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

6 carbon atoms? Specific examples of the aryl of 30 are phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene 3-yl, acenaphthylene-4-yl, acenaphthylene-5-yl, Fluoren-1-yl, Fluoren-2-yl, Fluoren-3-yl, Fluoren-4-yl, Fluoren-9-yl, Penalen-1-yl, Penalen-2-yl, 1 -Phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthene-1-yl, fluoranthene -2-yl, fluoranthene-3-yl, fluoranthene-7-yl, fluoranthene-8-yl, triphenylen-1-yl, triphenylen-2-yl, pyren-1-yl , Pyren-2-yl, pyren-4-yl, chryshen-1-yl, chryssen-2-yl, chryssen-3-yl, chryssen-4-yl, chrysene-5-yl, chrysene -6-yl, naphthace-1-yl, naphthace-2-yl, naphthace-5-yl, perylene-1-yl, perylene-2-yl, perylene-3-yl, pentacene- 1-day, pentacene-2-yl, pentacene-5-yl, pentacene-6-yl.

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

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 long as this reducing substance has a certain reducing property, various things are used, For example, alkali metal, alkaline-earth metal, rare earth metal, oxide of an alkali metal, halide of an alkali metal, oxide of an alkaline earth metal, halide of an alkaline earth metal At least one selected from the group consisting of oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals and organic complexes of rare earth metals can be preferably used.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (copper 2.28 eV), Rb (copper 2.16 eV) or Cs (copper 1.95 eV), Ca (copper 2.9 eV), Sr (copper Alkaline earth metals, such as 2.0-2.5 eV) or Ba (copper 2.52 eV), and it is especially preferable that a work function is 2.9 eV or less. Of these, the more preferable reducing substance is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, most preferably Cs. In particular, these alkali metals have a high reducing ability and a relatively small amount of addition to the material forming the electron transporting layer or the electron injecting layer can improve the luminescence brightness and extend the life of the organic EL device. Moreover, the combination of these 2 or more types of alkali metals is also preferable as a reducing substance whose work function is 2.9 eV or less, Especially the combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or Cs and Na Combinations of and K are preferred. By including Cs, reduction ability can be exhibited efficiently, and addition to the material which forms an electron carrying layer or an electron injection layer improves the luminescence brightness in an organic electroluminescent element, and prolongs lifetime.

<Cathode in organic electroluminescent element>

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 is a substance capable of injecting electrons into the organic layer efficiently. The same material as the material for forming the anode 102 can be used. Among them, metals such as tin, magnesium, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys (magnesium-silver alloys, Aluminum-lithium alloys such as magnesium-indium alloy and lithium fluoride / aluminum). In order to improve electron injection efficiency and improve device characteristics, an alloy containing lithium, sodium, potassium, cesium, calcium, magnesium or these low work function metals is effective. However, these low work function metals are often unstable in the atmosphere. In order to improve this point, for example, a method of doping a small amount of lithium, cesium or magnesium in the organic layer to use an electrode having high stability is known. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide can also be used. However, it is not limited to these.

In addition, for electrode protection, metals such as platinum, gold, silver, 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, hydrocarbons, etc. Laminating | stacking a system high molecular compound etc. is mentioned as a preferable example. The production method of these electrodes is not particularly limited as long as it can conduct, such as resistance heating, electron beam beam, sputtering, ion plating, and coating.

<Binder to be used in each layer>

The above materials used in the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer and the electron injection layer may form each layer alone. 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 And solvent-soluble resins such as polyurethane resins, and phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, and the like. .

<Production Method of Organic Electroluminescent Element>

Each layer constituting the organic EL device is a thin film by a method such as deposition method, resistive heating deposition, electron beam deposition, sputtering, molecular lamination method, printing method, spin coat method or cast method, coating method, etc. It can form by making it. There is no restriction | limiting in particular about the film thickness of each layer formed in this way, Although it can set suitably according to the property of a material, Usually, it is 2 nm? It is the range of 5000 nm. The film thickness can usually be measured by a crystal oscillation film thickness measuring device or the like. In the case of thinning using the vapor deposition method, the vapor deposition conditions differ depending on the kind of material, the crystal structure and the associative structure for the purpose of the film. Deposition conditions are generally boat heating temperature + 50? + 400 ° C., vacuum degree 10 ⁻⁶ ? 10 ^-3 kPa, deposition rate of 0.01? 50 nm / sec, substrate temperature-150? +300 degreeC, film thickness 2nm? It is preferable to set suitably in the range of 5 micrometers.

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

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

<Application example of organic electroluminescent element>

Moreover, this invention can be applied also to the display apparatus provided with organic electroluminescent element, the lighting apparatus provided with organic electroluminescent element, etc.

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

As a display apparatus, flexible displays, such as a panel display, such as a color flat panel display, and a flexible color organic electroluminescent (EL) display, etc. are mentioned (for example, Unexamined-Japanese-Patent No. 10-335066). , Japanese Unexamined Patent Publication No. 2003-321546, Japanese Unexamined Patent Publication No. 2004-281086, etc.). Moreover, as a display system of a display, a matrix and / or a segment system etc. are mentioned, for example. In addition, the matrix display and the segment display may coexist in the same panel.

The matrix means that pixels for display are arranged two-dimensionally, such as a lattice shape or a mosaic shape, and displays a character or an image by a set of pixels. The shape and size of the pixel is determined depending on the application. For example, a square pixel having one side of 300 μm or less is usually used for image and character display of a PC, a monitor, a television, and in the case of a large display such as a display panel, a pixel having a side order of mm is used. do. In the case of monochrome display, pixels of the same color may be arranged. In the case of color display, pixels of red, green and blue are displayed in a line. In this case, there are typically delta types and stripe types. The matrix driving method may be any one of a line sequential driving method and an active matrix. The linear sequential drive has an advantage of a simpler structure. In view of the operating characteristics, the active matrix may be superior to the active matrix.

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

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

Example

EMBODIMENT OF THE INVENTION Below, this invention is demonstrated in more detail based on an Example. First, the synthesis example of the anthracene derivative used in the Example is demonstrated below.

<Synthesis example of anthracene derivative represented by formula (1-6)>

[Formula 53]

<Synthesis of 4- (4- (anthracene-9-yl) phenyl) pyridine>

9-bromoanthracene (25.0 g), bispinacolatodiborone (27.0 g), Pd (dba) ₂ (1.7 g), tricyclohexylphosphine (1.6 g), potassium acetate (19.0 g), potassium carbonate ( The flask containing 14.0 g) and cyclopentyl methyl ether (200 mL) was heated and stirred at reflux 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 refluxed The mixture was heated and stirred for 2 hours at a temperature. After cooling the reaction liquid to room temperature, the target product was extracted with chlorobenzene. In this chlorobenzene solution, in order to remove the metal ion of a catalyst, the solution which melt | dissolved the ethylenediamine tetraacetic acid-4 sodium salt dihydrate equivalent to about equimolar with respect to the target compound in the appropriate amount of water (afterwards in EDTA-4Na aqueous solution) Was abbreviated), and liquid-separated. The solvent was distilled off under reduced pressure, and the precipitated solid was washed with methanol. Furthermore, it dissolved in chlorobenzene again and refine | purified by active alumina column chromatography (developing liquid: chlorobenzene / ethyl acetate mixed solvent). At this time, referring to the method described in `` Guidelines for Organic Chemistry Experiment (1) -Material Handling and Separation and Purification Method '', Chemical Drivers Publication, page 94, the ratio of ethyl acetate in the developing solution is gradually increased to elute the target product. I was. The solvent was distilled off under reduced pressure, and then washed with methanol to obtain 4- (4- (anthracene-9-yl) phenyl) pyridine (15.9 g).

<Synthesis of 4- (4- (10-bromoanthracene-9-yl) phenyl) pyridine>

A flask containing 4- (4- (anthracene-9-yl) phenyl) pyridine (8.0 g), N-bromosuccinimide (4.5 g), iodine (0.06 g) and chloroform (500 mL) was prepared at room temperature. Stirred for 18 hours. After adding an aqueous sodium sulfite solution and stopping the reaction, the solution was distilled off under reduced pressure. The precipitated solid was washed with methanol, followed by water and methanol, and then dissolved in chlorobenzene. Methanol was added to this solution, and it was reprecipitated to obtain 4- (4- (10-bromoanthracene-9-yl) phenyl) pyridine (9.1 g).

<Synthesis of Compound Represented by Formula (1-6)>

2- (3-bromophenyl) pyridine (2.8 g), bispinacolatodiborone (3.3 g), Pd (dppf) Cl ₂ (0.3 g), potassium acetate (3.5 g) and cyclopentylmethylether (20 mL ) And the flask was heated and stirred at reflux for 2 hours. Once cooled to room temperature, 4- (4- (10-bromoanthracene-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 heated and stirred at reflux for further 2 hours. After cooling the reaction liquid to room temperature, the solid in the liquid was collected by suction filtration, and then washed with methanol, followed by water and methanol. After washing, the mixture was purified by silica gel column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. The solvent was distilled off under reduced pressure, and then recrystallized from chlorobenzene to give a compound (3.1 g) represented by formula (1-6).

The glass transition temperature (Tg) by DSC measurement was 115 degreeC, and the energy gap which tangentially estimated the absorption edge of the absorption spectrum was 2.95 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

<Synthesis example of anthracene derivative represented by formula (1-11)>

[Formula 54]

<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), bispinacolatodiborone (5.5 g), Pd (dppf) Cl ₂ (3.2 g), potassium acetate (28.0 g) and cyclopentylmethyl The flask containing ether (60 mL) was heated and stirred for 1 hour and a half at reflux temperature. After cooling to room temperature once, toluene and EDTA-4Na aqueous solution were added and liquid-separated. After distilling off the solvent under reduced pressure, the solvent was purified by activated carbon column chromatography (developing solution: toluene) to prepare 3- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2. -Yl) naphthalen-1-yl) pyridine (30.1 g) was obtained.

<Synthesis of 3- (4- (anthracene-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), a flask containing Pd (dba) ₂ (0.3 g), tricyclohexylphosphine (0.3 g), potassium phosphate (6.8 g) and 1,2,4-trimethylbenzene (30 mL) was refluxed. It stirred by heating at temperature for 13 hours. After cooling to room temperature once, toluene and water were added and liquid-separated. After distilling off the solvent under reduced pressure, the solvent was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate mixed solvent) to obtain 3- (4- (anthracene-9-yl) naphthalen-1-yl) pyridine (4.1 g). Got. At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. The solvent was distilled off under reduced pressure.

<Synthesis of 3- (4- (10-bromoanthracene-9-yl) naphthalen-1-yl) pyridine>

3- (4- (anthracene-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, the reaction was stopped, and then toluene was added and liquid-separated. After distilling off the solution under reduced pressure, the solution was purified by a silica gel short column (developing solution: toluene / ethyl acetate mixed solvent (volume ratio = approximately 1/1)) to obtain 3- (4- (10-bromoanthracene-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), bispinacolatodiborone (23.4 g), Pd (dppf) Cl ₂ (1.9 g), potassium acetate (20.5 g) and cyclopentylmethylether (150 mL ) And the flask was heated and stirred at reflux for 1 hour. After cooling to room temperature once, toluene and EDTA-4Na aqueous solution were added and liquid-separated. After distilling off the solvent under reduced pressure, the product was purified by activated carbon column chromatography (developing solution: toluene) to obtain 3- (3- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2. -Yl) 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-bromo Anthracene-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), iso The flask containing propyl alcohol (2 ml) and water (2 ml) was heated and stirred at reflux for 9 hours. After cooling to room temperature once, toluene and water were added and liquid-separated. The solvent was distilled off under reduced pressure, and then purified by active alumina column chromatography (developing solution: toluene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. The solvent was distilled off under reduced pressure, and then recrystallized from toluene to obtain compound (0.3 g) represented by formula (1-11).

The glass transition temperature (Tg) by DSC measurement was 130 degreeC, and the energy gap tangentially estimated by the absorption edge of the absorption spectrum was 2.97 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

<Synthesis example of anthracene derivative represented by formula (1-15)>

(55)

3- (3-bromophenyl) pyridine (5.6 g), bispinacolatodiborone (6.6 g), Pd (dppf) Cl ₂ (0.6 g), potassium acetate (7.0 g) and cyclopentylmethyl ether (40 mL ) And the flask was heated and stirred at reflux for 2 hours. Once cooled to room temperature, 4- (4- (10-bromoanthracene-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 heated and stirred at reflux for further 5 hours. After cooling the reaction liquid to room temperature, the solid in the liquid was collected by suction filtration, and then washed with methanol, followed by water and methanol. After washing, the resultant was purified by active alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. After distilling off the solvent under reduced pressure, the solvent was recrystallized from chlorobenzene to obtain a compound (7.0 g) represented by Formula (1-15).

The glass transition temperature (Tg) by DSC measurement was 111 degreeC, and the energy gap which tangentially estimated the absorption edge of the absorption spectrum was 2.94 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

<Synthesis example of anthracene derivative represented by formula (1-19)>

(56)

<Synthesis of 4- (3- (anthracene-9-yl) phenyl) pyridine>

9-bromoanthracene (25.0 g), bispinacolatodiborone (27.0 g), Pd (dba) ₂ (2.8 g), tricyclohexylphosphine (2.7 g), potassium acetate (19.0 g), potassium carbonate ( The flask containing 14.0 g) and cyclopentyl methyl ether (200 mL) was heated and stirred at reflux for 12 hours. Once cooled to room temperature, 4- (3-bromophenyl) pyridine (27.0 g), Pd (PPh ₃ ) ₄ (3.3 g), t-butylalcohol (20 mL) and 1,2,4-trimethylbenzene (200 mL) was added and the mixture was further stirred under heating at reflux for 8 hours. After cooling the reaction liquid to room temperature, the solid precipitated by suction filtration was removed, an EDTA 4Na aqueous solution was added, and liquid separation was carried out. The oil obtained by distilling a solvent off under reduced pressure was refine | purified by silica gel column chromatography (developing liquid: toluene / ethyl acetate mixed solvent), and 4- (3- (anthracene-9-yl) phenyl) pyridine (24.6 g) was obtained. . At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product.

<Synthesis of 4- (3- (10-bromoanthracene-9-yl) phenyl) pyridine>

A flask containing 4- (3- (anthracene-9-yl) phenyl) pyridine (23.6 g), N-bromosuccinimide (13.3 g), iodine (0.09 g) and chloroform (500 mL) was prepared at room temperature. Stirred for 18 hours. After adding an aqueous sodium sulfite solution and separating the solution, the solution was distilled off under reduced pressure, and the oil thus obtained was purified by silica gel column chromatography (developing solution: toluene / ethyl acetate mixed solvent) to obtain 4- (3- (10-bro). Moanthracene-9-yl) phenyl) pyridine (26.6 g) was obtained. At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product.

<Synthesis of Compound Represented by Formula (1-19)>

2- (4-bromonaphthalen-1-yl) pyridine (6.8 g), bispinacolatodiborone (6.1 g), Pd (dppf) Cl ₂ (0.6 g), potassium acetate (7.1 g) and cyclopentylmethyl The flask containing ether (50 mL) was heated and stirred at reflux for 4 hours. Once cooled to room temperature, 4- (3- (10-bromoanthracene-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 heated and stirred at reflux for 4 hours. After cooling the reaction liquid to room temperature, toluene was added, the solid in the liquid was removed by suction filtration, and an EDTA 4Na aqueous solution was added to separate the liquid. 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 ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. Ethyl acetate was added to the oil obtained by distilling a solvent off under reduced pressure, and it precipitated, and collected by suction filtration. Moreover, for decolorization, activated carbon short column chromatography was performed and the compound (6.5g) shown by Formula (1-19) was obtained.

The glass transition temperature (Tg) by DSC measurement was 141 degreeC, and the energy gap which tangentially estimated the absorption edge of the absorption spectrum was 2.98 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

<Synthesis example of anthracene derivative represented by formula (1-24)>

(57)

4- (4-bromophenyl) pyridine (5.5 g), bispinacolatodiborone (6.4 g), Pd (dppf) Cl ₂ (0.6 g), potassium acetate (6.9 g) and cyclopentylmethyl ether (50 mL ), The flask was heated and stirred at reflux for 5 hours. Once cooled to room temperature, 4- (3- (10-bromoanthracene-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 heated and stirred at reflux for 4 hours. After cooling the reaction liquid to room temperature, chlorobenzene and EDTA-4Na aqueous solution were added and liquid-separated. The solution was distilled off under reduced pressure and purified by active alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. After distilling off the solvent under reduced pressure, it was further reprecipitated with chlorobenzene / methanol, and the compound (2.4g) represented by Formula (1-24) was obtained.

The glass transition temperature (Tg) by DSC measurement was 119 degreeC, and the energy gap which tangentially estimated the absorption edge of an absorption spectrum was 2.95 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

<Synthesis example of anthracene derivative represented by formula (1-36)>

(58)

3- (4-bromonaphthalen-1-yl) pyridine (3.0 g), bispinacolatodiborone (3.2 g), Pd (dppf) Cl ₂ (0.3 g), potassium acetate (3.5 g) and cyclopentylmethyl The flask containing ether (20 mL) was heated and stirred at reflux for 2 hours. Once cooled to room temperature, 4- (4- (10-bromoanthracene-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 heated and stirred at reflux for 8 hours. After cooling the reaction liquid to room temperature, the solid in the liquid was collected by suction filtration, and then washed with methanol, followed by water and methanol. After washing, the resultant was purified by active alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. After distilling off the solvent under reduced pressure, reprecipitation was carried out with chlorobenzene / methanol to obtain the compound (1.3 g) represented by the formula (1-36).

The glass transition temperature (Tg) by DSC measurement was 147 degreeC, and the energy gap which tangentially estimated the absorption edge of the absorption spectrum was 2.95 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

<Synthesis example of anthracene derivative represented by formula (1-27)>

[Chemical Formula 59]

<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), potassium phosphate (330.0 g), a flask containing xylene (1000 mL), tetrahydrofuran (300 mL), isopropyl alcohol (300 mL) and water (300 mL) was heated and stirred at reflux for 1.5 hours. After cooling the reaction solution to room temperature, water and ethyl acetate were added, and the resultant was filtered by suction with a Kiriyama funnel covered with celite. The obtained filtrate was separated, and the organic layer was washed with EDTA-4Na aqueous solution, followed by water. The solvent was distilled off under reduced pressure, and the obtained solid was washed with ethyl acetate. Furthermore, it refine | purified by silica gel column chromatography (developing liquid: chlorobenzene / heptane mixed solvent). At this time, the ratio of chlorobenzene in the developing solution was gradually increased to elute the target product. After fractionating a target substance, the solvent was distilled off under reduced pressure to obtain 9- (6-methoxynaphthalen-2-yl) anthracene (227.0 g).

<Synthesis of 6- (anthracene-9-yl) naphthalene-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) was charged at 175 ° C. Stirred for 4 hours. After cooling the reaction solution to room temperature, water was added to carry out heat washing, and solids were 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- (anthracene-9-yl) naphthalen-2-yl trifluoromethanesulfonate>

The flask containing 6- (anthracene-9-yl) naphthalene-2-ol (217.0 g) and pyridine (500 mL) was cooled in an ice bath to give trifluoromethanesulfonic anhydride (250.0 g). It dripped. After completion | finish of dripping, after stirring at room temperature overnight, water and chlorobenzene were added and liquid-separated. The solvent was distilled off under reduced pressure, and then purified by silica gel column chromatography (chlorobenzene). Furthermore, the solvent was distilled off under reduced pressure, and the obtained solid was heated and washed with heptane to obtain 6- (anthracene-9-yl) naphthalen-2-yl trifluoromethanesulfonate (206.0 g).

<Synthesis of 4- (6- (anthracene-9-yl) naphthalen-2-yl) pyridine>

6- (anthracene-9-yl) naphthalen-2-yl trifluoromethanesulfonate (27.0 g), 4-pyridineboronic acid (8.8 g), Pd (PPh ₃ ) ₄ (3.4 g), potassium phosphate (25.0 g), a flask containing xylene (150 mL), tetrahydrofuran (50 mL), isopropyl alcohol (50 mL) and water (50 mL) was heated and stirred at reflux for 3 hours and a half. After cooling the reaction liquid to room temperature, water and chlorobenzene were added and liquid-separated, and the organic layer was wash | cleaned with EDTA-4Na aqueous solution, and then water. The solvent was distilled off under reduced pressure, and the obtained solid was washed with ethyl acetate. Furthermore, it refine | purified by active alumina column chromatography (developing liquid: chlorobenzene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. After the target product was fractionated, the solvent was distilled off under reduced pressure, and the obtained solid was washed with warm heptane to obtain 4- (6- (anthracene-9-yl) naphthalen-2-yl) pyridine (19.0 g).

<Synthesis of 4- (6- (10-bromoanthracene-9-yl) naphthalen-2-yl) pyridine>

4- (6- (anthracene-9-yl) naphthalen-2-yl) pyridine (19.0 g), N-bromosuccinimide (10.6 g), iodine (0.09 g) and tetrahydrofuran (300 mL) The flask contained was stirred for 18 hours at room temperature. After adding an aqueous sodium sulfite solution and stirring vigorously, tetrahydrofuran was distilled off under reduced pressure. Subsequently, the solid was collected by suction filtration and washed with warm water. Furthermore, it refine | purified by active alumina column chromatography (developing liquid: chlorobenzene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. After fractionation of the target substance, the solvent was distilled off under reduced pressure, and the precipitated crystals were collected by suction filtration to obtain 4- (6- (10-bromoanthracene-9-yl) naphthalen-2-yl) pyridine (17.1 g). Got it.

<Synthesis of (10- (6- (pyridin-4-yl) naphthalen-2-yl) anthracene-9-yl) boronic acid>

A flask containing 4- (6- (10-bromoanthracene-9-yl) naphthalen-2-yl) pyridine (10.0 g) and tetrahydrofuran (200 mL) was placed in a dry ice / methanol bath at −70 ° C. or lower. Cooled to. 1.6M n-butyllithium hexane solution (15 ml) was dripped there, and trimethyl borate (3.6 ml) was dripped after stirring for 1 hour. After completion of the dropwise addition, the reaction solution was heated to room temperature, 1 M 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- (6- (pyridin-4-yl) naphthalen-2-yl) anthracene-9-yl) boronic acid (8.8 g). In addition, although the purity of (10- (6- (pyridin-4-yl) naphthalen-2-yl) anthracene-9-yl) boronic acid obtained here is not high, it used for the next process, without further refine | purifying.

<Synthesis of Compound Represented by Formula (1-27)>

(10- (6- (pyridin-4-yl) naphthalen-2-yl) anthracene-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-butylalcohol (10 mL) and water (5 mL ) And the flask was heated and stirred at reflux for 3 hours. After cooling the reaction liquid to room temperature, water and toluene were added and liquid-separated, and the organic layer was wash | cleaned with EDTA-4Na aqueous solution, and then water. The solvent was distilled off under reduced pressure, and then purified by active alumina column chromatography (developing solution: chlorobenzene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. Furthermore, after purifying by activated carbon column chromatography (developing liquid: toluene), the solvent was distilled off under reduced pressure, and then recrystallized from chlorobenzene to give a compound (1.4 g) represented by formula (1-27).

The glass transition temperature (Tg) by DSC measurement was 140 degreeC, and the energy gap which tangentially estimated the absorption edge of the absorption spectrum was 2.93 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

<Synthesis example of anthracene derivative represented by formula (1-54)>

(60)

(10- (6- (pyridin-4-yl) naphthalen-2-yl) anthracene-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-butylalcohol (2 mL) and water (2 mL ) And the flask was heated and stirred at reflux 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 in the order of EDTA-4Na aqueous solution, water, and methanol. Next, it refine | purified by activated alumina column chromatography (developing liquid: chlorobenzene), and refine | purified by activated carbon column chromatography (developing liquid: chlorobenzene) again. The solvent was distilled off under reduced pressure, and then recrystallized from chlorobenzene to give a compound (1.5 g) represented by formula (1-54).

The glass transition temperature (Tg) by DSC measurement was not observed, but the energy gap tangentially estimated by the absorption edge of the absorption spectrum was 2.96 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

<Synthesis example of anthracene derivative represented by formula (1-42)>

(61)

<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), potassium phosphate The flask containing (124.0 g), 1,2,4-trimethylbenzene (400 mL) and t-butyl alcohol (40 mL) was heated and stirred at reflux 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 in the order of EDTA-4Na aqueous solution, water, and methanol. The solid was dissolved in heated chlorobenzene, and suction filtration was performed using 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- (anthracene-9-yl) naphthalene-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) was charged at 175 ° C. Stirred 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 dissolved in heated chlorobenzene after heating and washing with methanol, and suction filtration was performed using a Kiriyama funnel covered with silica gel. The filtrate was distilled off under an appropriate amount under reduced pressure, heptane was added thereto, and reprecipitation was carried out to obtain 4- (anthracene-9-yl) naphthalen-1-ol (74.3 g).

<Synthesis of 4- (anthracene-9-yl) naphthalen-1-yl trifluoromethanesulfonate>

The flask containing 4- (anthracene-9-yl) naphthalene-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 | finish of dripping, after stirring at room temperature for 1 hour, water was added and the precipitated solid was collected by suction filtration. Methanol wash | cleaned the obtained solid, it melt | dissolved in toluene, and the suction filtration was performed by the Kiriyama funnel which covered with silica gel. The filtrate was distilled off under reduced pressure and then recrystallized from heptane to obtain 4- (anthracene-9-yl) naphthalen-1-yl trifluoromethanesulfonate (100.2 g).

<Synthesis of 4- (4- (anthracene-9-yl) naphthalen-1-yl) pyridine>

4- (Anthracene-9-yl) naphthalen-1-yl trifluoromethanesulfonate (27.0 g), 4-pyridineboronic acid (8.8 g), Pd (PPh ₃ ) ₄ (1.4 g), potassium phosphate (25.0 g), a flask containing xylene (200 mL), isopropyl alcohol (50 mL) and water (25 mL) was heated and stirred at reflux for 2 hours. After cooling the reaction liquid to room temperature, water and toluene were added and liquid-separated, and the organic layer was wash | cleaned with EDTA-4Na aqueous solution, and then water. The solid obtained by distilling a solvent off under reduced pressure was refine | purified by active alumina column chromatography (developing liquid: toluene / ethyl acetate mixed solvent), and 4- (4- (anthracene-9-yl) naphthalen-1-yl) pyridine ( 19.9 g) was obtained. At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product.

<Synthesis of 4- (4- (10-bromoanthracene-9-yl) naphthalen-1-yl) pyridine>

4- (4- (anthracene-9-yl) naphthalen-1-yl) pyridine (19.9 g), N-bromosuccinimide (11.1 g), iodine (0.07 g) and tetrahydrofuran (300 mL) The flask contained was stirred for 18 hours at room temperature. An aqueous sodium sulfite solution was added and stirred vigorously, followed by adding water and ethyl acetate to separate the solution. The solid obtained by distilling a solvent off under reduced pressure was refine | purified by active alumina column chromatography (developing liquid: toluene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. After fractionation of the target substance, heptane was added to the oily component obtained by distilling off the solvent under reduced pressure, and reprecipitation was carried out to obtain 4- (4- (10-bromoanthracene-9-yl) naphthalene-1- Yl) pyridine (22.2 g) was obtained.

<Synthesis of (10- (4- (pyridin-4-yl) naphthalen-1-yl) anthracene-9-yl) boronic acid>

A flask containing 4- (4- (10-bromoanthracene-9-yl) naphthalen-1-yl) pyridine (22.0 g) and tetrahydrofuran (200 mL) was dried in a dry ice / methanol bath at −70 ° C. or lower. Cooled to. 1.6 M n-butyllithium hexane solution (33 mL) was dripped there, and trimethyl borate (6.4 mL) was dripped after stirring for 1 hour. After completion of the dropwise addition, the reaction solution was raised to room temperature, 1 M 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) anthracene-9-yl) boronic acid (18.0 g). In addition, although the purity of (10- (4- (pyridin-4-yl) naphthalen-1-yl) anthracene-9-yl) boronic acid obtained here is not high, it used for the next process, without further refine | purifying.

<Synthesis of Compound Represented by Formula (1-42)>

(10- (4- (pyridin-4-yl) naphthalen-1-yl) anthracene-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-butylalcohol (25 mL) and tetrahydrofuran ( The flask containing 50 mL) was heated and stirred at reflux for 1 hour. After cooling the reaction liquid to room temperature, water was added and the precipitated solid was obtained by suction filtration. The obtained solid was wash | cleaned with EDTA-4Na aqueous solution, and then water. Furthermore, after wash | cleaning with methanol, then ethyl acetate, it refine | purified by active alumina column chromatography (developing liquid: chlorobenzene / ethyl acetate mixed solvent). At this time, the ratio of ethyl acetate in the developing solution was gradually increased to elute the target product. After distilling off a suitable amount of solvents under reduced pressure, ethyl acetate was added and reprecipitation was carried out to obtain a compound (6.3 g) represented by formula (1-42).

The glass transition temperature (Tg) by DSC measurement was not observed, but the energy gap tangentially estimated by the absorption edge of the absorption spectrum was 2.96 eV.

Moreover, the structure of the anthracene derivative obtained by NMR measurement was confirmed.

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

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

As for the method of measuring the energy gap, first, a thin film was produced by an evaporator, the absorption curve of the thin film was measured using an ultraviolet-visible absorbance meter, and then tangent to the rising point on the short wavelength side of the absorption curve was obtained. By substituting the wavelength of an intersection into the following formula, an energy gap can be calculated | required.

Energy gap = 1240 ÷ intersection wavelength (nm)

For example, when the value obtained by drawing a tangent line 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 JP-A-2009-173642 (typically exemplifying the compound of formula (1-6) below) is smaller than 2.90 eV, and in the blue light emitting device, the present invention It can be seen that the compound of has an excellent confinement effect of excitons.

[Formula 62]

Hereinafter, although an Example is shown in order to demonstrate this invention further in detail, this invention is not limited to these.

Example 1? 9 and Comparative Example 1? The luminance maintained at 90% or more of the initial luminance when the electroluminescent element according to 4 was fabricated and the constant current was driven at the current density at which the driving start voltage (V) and the luminance of 2000 cd / m 2 in the constant current driving test were obtained, respectively. The time (hours) to measure was measured. Hereinafter, an Example and a comparative example are explained in full detail.

Example 1 produced? 9 and Comparative Example 1? The material structure of each layer in the electroluminescent element which concerns on 4 is shown in following Table 2. Moreover, in all, the negative electrode was comprised with 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, 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) naphthalene-1- Yl) anthracene, compound (E) is 9,10-bis (4- (pyridin-4-yl) phenyl) anthracene, compound (F) is 9,10-bis (4- (pyridin-2-yl) naphthalene- 1-yl) anthracene and "Liq" are 8-quinolinolithium. The chemical structure is shown below.

(63)

<Example 1>

A 26 mm x 28 mm x 0.7 mm glass substrate (manufactured by OptoScience Co., Ltd.), which was polished to 150 nm by ITO formed into a film at a thickness of 180 nm by sputtering, was used as a transparent support substrate. The transparent support substrate is fixed to a substrate holder of a commercially available deposition apparatus (manufactured by Vacuum Pore Co., Ltd.), and a molybdenum deposition boat containing HI, a molybdenum deposition boat containing NPD, and a molybdenum containing compound (A) Evaporation boat, molybdenum evaporation boat with compound (B), molybdenum evaporation boat with compound (1-6) of the present invention, molybdenum evaporation boat with quinolinol lithium (Liq), magnesium The tungsten vapor deposition boat and silver tungsten vapor deposition boat were attached.

The following each layer was formed sequentially on the ITO film | membrane of a transparent support substrate. The vacuum vessel was decompressed to 5 × 10 ⁻⁴ Pa, and the deposition boat containing HI was first heated to deposit a film thickness of 40 nm to form a hole injection layer, and then the deposition boat containing NPD was formed. It heated and deposited so that it might become a film thickness of 30 nm, and formed the hole transport layer. Next, the vapor deposition boat containing the compound (A) and the vapor deposition boat containing the compound (B) were simultaneously heated to be deposited so as to have a thickness of 35 nm to form a light emitting layer. The deposition rate was adjusted so that the weight ratio of compound (A) and compound (B) was approximately 95 to 5. Next, the evaporation boat containing compound (1-6) was heated, and it deposited so that it might become a film thickness of 15 nm, and the electron carrying layer was formed. The deposition rate of each layer is 0.01? 1 nm / second.

Thereafter, the vapor deposition boat containing quinolinolithium (Liq) was heated to have a film thickness of 0.01? Deposited at a deposition rate of 0.1 nm / second. Subsequently, the boat containing magnesium and the boat containing silver were simultaneously heated to be deposited so as to have a film thickness of 100 nm to form a cathode. At this time, the deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10 to 1, and the cathode was formed so that the deposition rate was 0.1 nm to 10 nm to obtain an organic EL device.

When a direct current voltage is 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 can be obtained. Moreover, the constant current drive test was done by the current density for obtaining initial stage luminance of 2000 cd / m <2>. As a result, the driving start voltage was 5.24 V, and the time for maintaining the luminance above 90% (1800 cd / m 2) 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 Compound (1-6) was changed to Compound (1-11). A constant current drive test was conducted with a current density for obtaining an initial luminance of 2000 cd / m 2 using the ITO electrode as the anode and the magnesium / silver electrode as the cathode. As a result, the driving start voltage was 5.20 V, and the time for maintaining the brightness | luminance of 90% (1800 cd / m <2>) or more of initial luminance was 11 hours.

<Example 3>

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

<Example 4>

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

<Example 5>

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

<Example 6>

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

<Example 7>

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

<Example 8>

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

<Example 9>

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

<Comparative Example 1>

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

<Comparative Example 2>

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

<Comparative Example 3>

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

<Comparative Example 4>

An organic EL device was obtained in the same manner as in Example 1 except that Compound (1-6) was changed to Compound (F). A constant current drive test was conducted with a current density for obtaining an initial luminance of 2000 cd / m 2 using the ITO electrode as the anode and the magnesium / silver electrode as the cathode. As a result, the driving 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 shows Example 1? 9, Comparative Example 1? The test result of the electroluminescent element concerning 4 is put together.

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

100 organic electroluminescent devices
101 boards
102 anode
103 hole injection layer
104 hole transport layer
105 light emitting layer
106 electron transport layer
107 electron injection layer
108 cathode

Claims (20)

Anthracene derivative represented by following formula (1).
[Formula 1]

In said formula (1), R <^1> , R <^2> , R <^3> and R <^4> are respectively independently hydrogen, C1-C? 6 alkyl, 3? 6 cycloalkyl or C 6? 20 is aryl, and A and B are each independently the following formula (Py-1)? It is group represented by either of formula (Py-12), but A and B are not the same structure.
(2)

The method of claim 1,
In said formula (1), R <^1> , R <^2> , R <^3> and R <^4> are hydrogen, A and B are respectively independently said Formula (Py-1)? An anthracene derivative which is a group represented by either of formula (Py-12), and A and B are not the same structure. The method of claim 1,
In said formula (1), R <^1> , R <^2> , R <^3> and R <^4> are hydrogen, and one of A and B is said Formula (Py-1)? Is a group represented by any of formula (Py-9), and the other is a said formula (Py-1)? An anthracene derivative which is a group represented by either of formula (Py-12), and A and B are not the same structure. The method of claim 1,
In said formula (1), R <^1> , R <^2> , R <^3> and R <^4> are hydrogen, and one of A and B is said Formula (Py-1)? Is a group represented by any of formula (Py-3), and the other is a said formula (Py-4)? Anthracene derivative which is a group represented by any of formula (Py-12). The method of claim 1,
In said formula (1), R <^1> , R <^2> , R <^3> and R <^4> are hydrogen, and one of A and B is said Formula (Py-4)? Is a group represented by any of formula (Py-9), and the other is a said formula (Py-7)? Anthracene derivative which is a group represented by any of formula (Py-12). The method of claim 1,
Anthracene derivative represented by following formula (1-6).
(3)

The method of claim 1,
Anthracene derivative represented by following formula (1-11).
[Chemical Formula 4]

The method of claim 1,
Anthracene derivative represented by following formula (1-15).
[Chemical Formula 5]

The method of claim 1,
Anthracene derivative represented by following formula (1-19).
[Formula 6]

The method of claim 1,
Anthracene derivative represented by following formula (1-24).
[Formula 7]

The method of claim 1,
Anthracene derivative represented by following formula (1-36).
[Chemical Formula 8]

The method of claim 1,
Anthracene derivative represented by following formula (1-27).
[Formula 9]

The method of claim 1,
Anthracene derivative represented by following formula (1-42).
[Formula 10]
The method of claim 1,
Anthracene derivative represented by following formula (1-54).
(11)

The electron transport material containing the anthracene derivative as described in any one of Claims 1-14. A pair of electrodes consisting of an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron transport layer and / or electrons disposed between the cathode and the light emitting layer and containing the electron transport material according to claim 15. An organic electroluminescent device having an injection layer. 17. The method of claim 16,
At least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of a quinolinol-based metal complex, a pyridine derivative, a bipyridine derivative, a phenanthroline derivative, a borane derivative and a benzimidazole derivative Organic electroluminescent device. The method according to claim 16 or 17,
At least one of the electron transport layer and the electron injection layer may further be an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, an halide of an alkaline earth metal, an oxide of a rare earth metal, or a rare earth. An organic electroluminescent device containing at least one selected from the group consisting of a halide of a metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. The display device 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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