JP2015203027A - Anthracene derivative and organic el element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic EL element excellent in driving voltage and durability.SOLUTION: There is provided an organic EL element produced by using anthracene derivative shown below which is self-organized as a material for at least one layer of a plurality of layers constituting an element.

Description

  The present invention relates to an organic EL element that has been used as a thin screen for portable devices and car audios and is expected to be used for thin televisions and next-generation lighting.

  As this organic electroluminescence element, an element composed of anode / hole transport layer / light emitting layer / electron transport layer / cathode is known. The hole transport layer has a function of transporting holes injected from the anode to the light emitting layer, and one electron transport layer transports electrons injected from the cathode to the light emitting layer. By inserting these layers between the light emitting layer and both electrodes, it is known that luminous efficiency and durability are improved, and organic compounds suitable for each layer have been studied extensively.

  For example, anthracene derivatives having a pyridine ring in the molecule have been reported to form a stable electron transport layer that lowers the driving voltage of a light emitting element and extends the lifetime of the element (Patent Document 1, Patent Document 2, Patent) Document 3 and Patent document 4).

  In addition, developments that expect various effects using molecular self-assembly have been reported. Examples of cases where self-organization is used in the wet process of organic EL elements include light emission polarization using a material self-organized in a disk shape by hydrogen bonding (Patent Document 5), and aliphatic groups using silanol groups or thiol groups. In order to improve adhesiveness and reduce dark spots (Patent Document 6), or improve the liquid repellency of the surface of the organic ultra-thin film pattern by inkjet method. Using a silane compound, self-organization is performed on an electrode (Patent Document 7 and Patent Document 8), or a microporous structure that accommodates each element layer in order is stacked by self-organization (Patent Document 9). However, none of these techniques attempt to lower the drive voltage or extend the life.

  Examples of using self-organization of wet processes other than organic EL devices include nano-sizes utilizing π-π stacking using the planarity of aromatic rings and the amphipathic properties of hydrophilic and hydrophobic substituents. Although there is development of a photoconductive material for forming the structure (Patent Document 10), it does not relate to lowering the voltage and extending the life of the organic EL element.

  Furthermore, in order to stabilize the organic film of the organic EL element produced by a dry process, a method of heating the substrate during element production or the element after production has been developed. Is there any effect of lowering the driving voltage? , Even small (Patent Document 11, Patent Document 12, Patent Document 13, Patent Document 14).

  In addition, there is an example (Patent Document 15) in which the hole mobility of an organic transistor material is increased by introducing an alkyl substituent into an anthracene oligomer. However, by directly substituting an alkyl group into an oligoanthracene skeleton having high planar continuity, π -It has a structure that does not inhibit π stacking, and is a technology different from organic EL devices that reduce the planar continuity of the aromatic ring in order to adjust the HOMO and LUMO levels of the molecule. It does not relate to a decrease in driving voltage or a longer life.

  Similarly, alkylhexabenzocoronene has been reported as an example of an organic transistor material in which an alkyl group is directly introduced into an aromatic ring, and it has been reported that an alkyl group placed at an appropriate position improves charge mobility. (Patent Document 16). On the other hand, even if an alkyl group is directly introduced into chrysene, the carrier mobility cannot be increased as compared with the case where an aromatic ring substituent is introduced (Patent Document 17). Since the desired orientation direction of the aromatic ring plane of the material used for the organic transistor is perpendicular to the substrate, the effect of such self-organization by the alkyl group is for an organic EL material that moves charge in the direction perpendicular to the substrate. Not desirable. Therefore, it cannot be predicted that the self-organization technique in the organic transistor functions effectively for charge transfer in the case of an organic EL material in which aromatic rings are not easily brought close to each other.

International Publication No. 2007/086552 JP 2009-173642 A JP 2003-146951 A JP 2005-170911 A JP 2003-277741 A JP 2006-210125 A JP 2007-134348 A Japanese Patent Laid-Open No. 2003-092181 JP 2007-109524 A JP 2011-102271 A JP-A-5-18264 Japanese Patent Laid-Open No. 10-284248 Japanese Patent Laid-Open No. 11-40352 JP 2000-311784 A JP 2004-107257 A JP 2006-100592 A JP 2010-118415 A

  As described above, there are few conventional light emitting materials, hole transport materials, and electron transport materials in the organic EL device that have both long durability and low driving voltage. Crystallization due to heat generated from the element due to long-time energization shortens the lifetime of the element, and when used as an electron transport material, the material itself emits light and color purity is reduced. In order to suppress the above, the material having improved amorphous property has a problem in driving voltage. An object of the present invention is to provide an organic EL material capable of extending the element lifetime, suppressing an increase in voltage during driving, and reducing the driving voltage.

  The present inventors have found that a derivative in which a linear or linear aliphatic substituent is introduced into an anthracene having a pyridine ring can be self-assembled, and that the derivative is used as an electron transporting material. The inventors have found that the above problems can be solved, and have completed the following invention.

（一般式（１）中、
１ａ、１ｂ、２ａ、２ｂ、３ａ、３ｂ、４ａおよび４ｂは、それぞれ独立して、０または１であり、少なくとも１つは１であり、
Ａｒ^１１、Ａｒ^１２、Ａｒ^２１、Ａｒ^２２、Ａｒ^３１、Ａｒ^３２、Ａｒ^４１およびＡｒ^４２は、それぞれ独立して、置換もしくは無置換の、フェニレン、ナフタレンジイル、アントラセンジイル、またはピリジンジイルであり、少なくとも１つはピリジンジイルであり、
１ｃ、２ｃ、３ｃおよび４ｃは、それぞれ独立して、１〜５の整数であり、
Ｒ^１〜Ｒ^４は、それぞれ独立して、水素、置換もしくは無置換の脂肪族基、または、置換もしくは無置換の炭素数８〜２６の実質的に直鎖または直鎖の脂肪族基であり、少なくとも１つは置換もしくは無置換の炭素数８〜２６の実質的に直鎖または直鎖の脂肪族基であり、該実質的に直鎖または直鎖の脂肪族基の任意の炭素は−Ｏ−、−ＳｉＲ_２−（Ｒは炭素数１〜４のアルキル）またはシクロヘキサンジイルに置き換わってもよいが、−Ｏ−、−ＳｉＲ_２−、シクロヘキサンジイル、またはこれらの結合体が連続して置き換わることはなく、そして、
ｎおよびｍは、それぞれ独立して、１〜４の整数である。） [1]
Anthracene derivatives represented by the following general formula (1).

(In general formula (1),
1a, 1b, 2a, 2b, 3a, 3b, 4a and 4b are each independently 0 or 1, at least one is 1,
Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ²² , Ar ³¹ , Ar ³² , Ar ⁴¹ and Ar ⁴² are each independently substituted or unsubstituted phenylene, naphthalenediyl, anthracenediyl, or pyridinediyl; At least one is pyridinediyl;
1c, 2c, 3c and 4c are each independently an integer of 1 to 5,
R ^{1 to} R ⁴ are each independently hydrogen, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted substantially linear or linear aliphatic group having 8 to 26 carbon atoms. , At least one is a substituted or unsubstituted, substantially linear or linear aliphatic group having 8 to 26 carbon atoms, and any carbon of the substantially linear or linear aliphatic group is- O—, —SiR ₂ — (R is alkyl having 1 to 4 carbon atoms) or cyclohexanediyl may be substituted, but —O—, —SiR ₂ —, cyclohexanediyl, or a combination thereof is successively substituted. And nothing
n and m are each independently an integer of 1 to 4. )

[2]
1c is 1, R ¹ is hydrogen,
2c is 1 or 2, n is 1 or 2,
3c is 1, R ³ is hydrogen,
4a and 4b are 0, 4c is 1, m is 1, R ⁴ is hydrogen,
The substituent when Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ²² , Ar ³¹ and Ar ³² are substituted is alkyl, and
When R ² is substituted, the substituent is alkyl, cycloalkyl, aryl, or halogen;
The anthracene derivative according to the above [1] (see the following formula (2-a)).

[3]
1a and 1b are 1, Ar ¹¹ and Ar ³¹ are the same, Ar ¹² and Ar ³² are the same, and
2c is 1 and n is 1.
The anthracene derivative according to the above [2] (see the following formula (2-b)).

[4]
2b is 0,
When Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ³¹ and Ar ³² are substituted, the substituent is alkyl having 1 to 4 carbon atoms, and
R ² is a substituted or unsubstituted substantially linear or linear aliphatic group having 8 to 26 carbon atoms, and when substituted, the substituent is alkyl having 1 to 4 carbon atoms, cyclohexyl, phenyl , Naphthyl, anthracenyl, or fluorine,
The anthracene derivative according to the above [3] (see the following formula (2-c)).

[5]
Ar ¹¹ and Ar ³¹ are phenylene, Ar ¹² and Ar ³² are pyridinediyl,
Ar ²¹ is unsubstituted phenylene, naphthalenediyl, anthracenediyl, or pyridinediyl, and
R ² is unsubstituted straight chain alkyl having 8 to 20 carbon atoms,
The anthracene derivative according to the above [4] (see the following formula (2-d1)).

[6]
Ar ¹¹ , Ar ¹² , Ar ³¹ and Ar ³² are pyridinediyl;
Ar ²¹ is unsubstituted phenylene, naphthalenediyl, anthracenediyl, or pyridinediyl, and
R ² is unsubstituted straight chain alkyl having 8 to 20 carbon atoms,
The anthracene derivative according to the above [4] (see the following formula (2-d2)).

[7]
An anthracene derivative according to the above [5] or [6], wherein 2a is 1 and Ar ²¹ is phenylene (see the following formula (2-e1) or formula (2-e2)).

[8]
An anthracene derivative according to the above [5] or [6], wherein 2a is 0 (see the following formula (2-f1) or formula (2-f2)).

[9]
The anthracene derivative according to the above [7] or [8], wherein R ² is linear alkyl having 10 to 14 carbon atoms.

[10]
1c is 1 or 2,
2b is 0, 2c is 1, n is 1, R ² is hydrogen,
3c is 1, R ³ is hydrogen,
4a and 4b are 0, 4c is 1, m is 1, R ⁴ is hydrogen,
The substituent when Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ³¹ and Ar ³² are substituted is alkyl, and
The substituent when R ¹ is substituted is alkyl, cycloalkyl, aryl, or halogen,
The anthracene derivative according to the above [1] (see the following formula (3-a)).

[11]
1a is 1, 1c is 1,
2a is 0,
3a and 3b are 1,
When Ar ¹¹ , Ar ¹² , Ar ³¹ and Ar ³² are substituted, the substituent is alkyl having 1 to 4 carbon atoms, and
R ¹ is a substituted or unsubstituted substantially linear or linear aliphatic group having 8 to 26 carbon atoms, and when substituted, the substituent is alkyl having 1 to 4 carbon atoms, cyclohexyl, phenyl , Naphthyl, anthracenyl, or fluorine,
The anthracene derivative according to the above [10] (see the following formula (3-b)).

[12]
Ar ¹¹ , Ar ¹² , Ar ^31, and Ar ³² are each independently unsubstituted phenylene, naphthalenediyl, anthracenediyl, or pyridinediyl, and at least one is pyridinediyl, the above [11] The anthracene derivative described.

[13]
Ar ¹¹ , Ar ¹² and Ar ³¹ are phenylene, Ar ³² is pyridinediyl, and
R ¹ is unsubstituted straight chain alkyl having 8 to 20 carbon atoms,
The anthracene derivative according to the above [12] (see the following formula (3-c)).

[14]
The anthracene derivative according to the above [13], wherein R ¹ is linear alkyl having 10 to 14 carbon atoms.

[15]
Formula (1-1), Formula (1-7), Formula (1-37), Formula (1-43), Formula (1-61), Formula (1-534), Formula (1-535), The anthracene derivative according to the above [1], represented by formula (1-690) or formula (1-691).

[16]
A self-assembled material of an anthracene derivative according to any one of [1] to [15].

[17]
An electron transport material containing the self-organizing material according to [16] above.

[18]
An organic electroluminescent element comprising a pair of electrodes composed of an anode and a cathode, and an organic layer containing the anthracene derivative according to any one of [1] to [15].

[19]
(1) forming an organic layer containing the anthracene derivative by vapor deposition at 0.01 to 20.0 nm / second, and / or (2) during or after the production of the organic electroluminescent device, The organic electroluminescent element according to the above [18], which contains an anthracene derivative that is self-assembled by performing a heat treatment in a temperature range not higher than the lowest glass transition temperature Tg among the materials constituting the element.

[20]
A pair of electrodes comprising an anode and a cathode, a light emitting layer disposed between the pair of electrodes, an electron disposed between the cathode and the light emitting layer and containing the electron transport material according to the above [17] An organic electroluminescent device having a transport layer and / or an electron injection layer.

[21]
At least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of quinolinol-based metal complexes, pyridine derivatives, bipyridine derivatives, phenanthroline derivatives, borane derivatives, and benzimidazole derivatives. Organic electroluminescent element as described in said [20].

[22]
At least one of the electron transport layer and the electron injection layer may further include an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes, Organic electroluminescent element as described in said [20] or [21].

[23]
The display apparatus provided with the organic electroluminescent element as described in any one of said [18]-[22].

[24]
The illuminating device provided with the organic electroluminescent element as described in any one of said [18]-[22].

  The anthracene derivative according to the present invention can be self-assembled by vapor deposition or heating. In addition, by forming each layer of the organic EL element with such a self-organized anthracene derivative, it is possible to extend the lifetime of the element, suppress an increase in voltage during driving, and reduce a driving voltage.

  The inventors of the present invention, the anthracene derivative according to the present invention is self-organized by collision between molecules during deposition and molecules on the substrate or the substrate on which the film is formed, or heating during or after device fabrication, I think that the degree of organization will be raised. Self-organization is defined as the formation of a thermodynamically stable ordered structure by the deposition or heating of molecules in a random state as described above. This ordering is thought to be affected by intermolecular forces between aliphatic groups, and as a result, the molecules can be oriented while suppressing the crystallization of anthracene derivatives. I believe that. The energy required for ordering the molecules is the collision energy between molecules with kinetic energy during deposition and molecules deposited on the substrate or the substrate, thermal energy from the substrate, or externally after deposition. The given thermal energy can be used.

  In particular, it is thought that aromatic rings are close to each other without increasing the plane continuity of the aromatic rings in the anthracene derivative by self-organization by the interaction between the aliphatic groups, and as a result, orbitals involved in charge transfer. It is considered that the driving voltage of the organic EL element can be lowered by orienting and reducing the energy required for charge transfer. In addition, the organic layer that is ordered into a stable structure by thermal energy is considered to be able to extend the lifetime of the organic EL element because the morphology is not affected by the thermal energy of the element that generates heat by energization for a long time. ing.

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

（一般式（１）中、
１ａ、１ｂ、２ａ、２ｂ、３ａ、３ｂ、４ａおよび４ｂ（以下１ａ〜４ｂと略す）は、それぞれ独立して、０または１であり、少なくとも１つは１であり、
Ａｒ^１１、Ａｒ^１２、Ａｒ^２１、Ａｒ^２２、Ａｒ^３１、Ａｒ^３２、Ａｒ^４１およびＡｒ^４２（以下Ａｒ^１１〜Ａｒ^４２と略す）は、それぞれ独立して、置換もしくは無置換の、フェニレン、ナフタレンジイル、アントラセンジイル、またはピリジンジイルであり、少なくとも１つはピリジンジイルであり、
１ｃ、２ｃ、３ｃおよび４ｃ（以下１ｃ〜４ｃと略す）は、それぞれ独立して、１〜５の整数であり、
Ｒ^１〜Ｒ^４は、それぞれ独立して、水素、置換もしくは無置換の脂肪族基、または、置換もしくは無置換の炭素数８〜２６の実質的に直鎖または直鎖の脂肪族基であり、少なくとも１つは置換もしくは無置換の炭素数８〜２６の実質的に直鎖または直鎖の脂肪族基であり、該実質的に直鎖または直鎖の脂肪族基の任意の炭素は−Ｏ−、−ＳｉＲ_２−（Ｒは炭素数１〜４のアルキル）またはシクロヘキサンジイルに置き換わってもよいが、−Ｏ−、−ＳｉＲ_２−、シクロヘキサンジイル、またはこれらの結合体が連続して置き換わることはなく、そして、
ｎおよびｍは、それぞれ独立して、１〜４の整数である。） 1. Anthracene derivative represented by general formula (1) The present invention is an anthracene derivative represented by the following general formula (1).

(In general formula (1),
1a, 1b, 2a, 2b, 3a, 3b, 4a and 4b (hereinafter abbreviated as 1a to 4b) are each independently 0 or 1, and at least one is 1,
Ar ^{11, Ar 12,} (hereinafter referred to as ^{Ar 11 ~Ar 42) Ar 21,} Ar 22, Ar 31, Ar 32, Ar 41 and ^{Ar 42} are each independently a substituted or unsubstituted phenylene, naphthalene-diyl , Anthracenediyl, or pyridinediyl, at least one is pyridinediyl,
1c, 2c, 3c and 4c (hereinafter abbreviated as 1c to 4c) are each independently an integer of 1 to 5,
R ^{1 to} R ⁴ are each independently hydrogen, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted substantially linear or linear aliphatic group having 8 to 26 carbon atoms. , At least one is a substituted or unsubstituted, substantially linear or linear aliphatic group having 8 to 26 carbon atoms, and any carbon of the substantially linear or linear aliphatic group is- O—, —SiR ₂ — (R is alkyl having 1 to 4 carbon atoms) or cyclohexanediyl may be substituted, but —O—, —SiR ₂ —, cyclohexanediyl, or a combination thereof is successively substituted. And nothing
n and m are each independently an integer of 1 to 4. )

The following four types of substituents substituted with anthracene will be described using the following abbreviations.
^{_{"(R 1) 1c - (Ar}} 12) 1b - (Ar 11) 1a - " = "SUB1-"
“(R ² ) _2c − (Ar ²² ) _2b − (Ar ²¹ ) _2a −” = “SUB ₂ −”
“(R ³ ) _3c − (Ar ³² ) _3b − (Ar ³¹ ) _3a −” = “SUB ₃ −”
^{_{"(R 4) 4c - (Ar}} 42) 4b - (Ar 41) 4a - " = "SUB4-"

<For ^Ar 11 ^{~Ar 42>}
Phenylene is 1,2-, 1,3- or 1,4-phenylene, with 1,4-phenylene being preferred.
Naphthalenediyl is 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 2,3-, 2,6- or 2 , 7-naphthalenediyl, preferably 1,3-, 1,4-, 1,5-, 2,6- or 2,7-naphthalenediyl, 1,4-, 2,6- or 2,7 -Naphthalenediyl is particularly preferred.
Anthracenediyl is 1,2-, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-2, , 3-, 2,6-, 2,7-, 2,9-, 2,10- or 9,10-anthracenediyl, 1,2-, 1,3-, 1,4-, 1, 5-, 1,6-, 1,7-, 1,8-, 1,9-, 1,10-, 2,3-, 2,6-, 2,7-, 2,9-, 2, 10- or 9,10-anthracenediyl, 2,6- or 9,10-anthracenediyl being preferred.
Pyridinediyl is 2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-pyridinediyl, 2,4-, 2,5-, 2, 6- or 3,5-pyridinediyl is preferred.

<Substituents to Ar ^{11 to} Ar ⁴² >
Ar ^{11 to} Ar ⁴² may be substituted, and examples of the substituent include alkyl, which may be linear or branched, such as linear alkyl having 1 to 24 carbon atoms or 3 to 3 carbon atoms. There are 24 branched chain alkyls. Preferred alkyl is alkyl having 1 to 18 carbons (branched alkyl having 3 to 18 carbons). More preferable alkyl is alkyl having 1 to 12 carbons (branched alkyl having 3 to 12 carbons). More preferable alkyl is alkyl having 1 to 6 carbons (branched alkyl having 3 to 6 carbons). Particularly preferred alkyl is alkyl having 1 to 4 carbon atoms (branched alkyl having 3 to 4 carbon atoms).

  Specific examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, n-pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, and 1-methyl. Pentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, t-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propyl Pentyl, n-nonyl, 2,2-dimethylheptyl, 2,6-dimethyl-4-heptyl, 3,5,5-trimethylhexyl, n-decyl, n-undecyl, 1-methyldecyl, n-dodecyl, n- Tridecyl, 1-hexylheptyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl Le, n- octadecyl, such as n- eicosyl, and the like.

<For ^R 1 ^{~R 4>}
The aliphatic group is an alkyl group, an alkenyl group, or an alkynyl group, and may be either a straight chain or a branched chain. Examples thereof include straight-chain alkyl having 1 to 26 carbon atoms or branched alkyl having 3 to 26 carbon atoms, preferably alkyl having 1 to 18 carbon atoms (branched alkyl having 3 to 18 carbon atoms), Alkyl having 1 to 12 (branched alkyl having 3 to 12 carbons) is more preferable, alkyl having 1 to 6 carbons (branched alkyl having 3 to 6 carbons) is further preferable, and having 1 to 4 carbons. Alkyl (C3-C4 branched alkyl) is particularly preferred. Moreover, the alkenyl group or alkynyl group of the same carbon number as these illustrated alkyl is mention | raise | lifted. Furthermore, the aliphatic group may contain 1 to 3 carbon-carbon double bonds or carbon-carbon triple bonds, may contain 1 or 2, and may contain one.

  The substantially linear or linear aliphatic group having 8 to 26 carbon atoms is an alkyl group, an alkenyl group or an alkynyl group, and examples thereof include a substantially linear or linear alkyl group having 8 to 26 carbon atoms. A substantially straight-chain or straight-chain alkyl having 8 to 20 carbon atoms is preferable, a substantially straight-chain or straight-chain alkyl having 8 to 14 carbon atoms is more preferable, and a substantially straight-chain having 10 to 14 carbon atoms is substantially straight. More preferred are chain or straight chain alkyls. Moreover, the alkenyl group or alkynyl group of the same carbon number as these illustrated alkyl is mention | raise | lifted.

  The “substantially linear aliphatic group” is an aliphatic group in which a short side chain (branched chain) such as an alkyl group having 1 to 3 carbon atoms is bonded to the main chain. Is 50% or less of the total number of carbons (carbon number of the main chain is 50% or more), preferably 30% or less (main chain is 70% or more), more preferably 20% or less (main chain is 80% or more). Means things. In addition, when a long side chain such as a straight-chain alkyl group having 6 to 10 carbon atoms is bonded to the main chain, the above rules are followed.

  First, the case of short side chain bonding will be described more specifically. For example, in the case of an aliphatic group having 20 to 26 carbon atoms, “substantially straight chain” means 1 to 3 carbon atoms with respect to the main chain. It means that 1 to 4 side chains (branched chains) of the alkyl group may be bonded. However, the t-butyl group (4 carbon atoms) is exceptionally calculated as an alkyl chain having 2 carbon atoms included in the “alkyl group having 1 to 3 carbon atoms” (the same applies hereinafter). In the case of an aliphatic group having 17 to 19 carbon atoms, 1 to 3 side chains (branched chains) of an alkyl group having 1 to 3 carbon atoms may be bonded to the main chain. In the case of 16 aliphatic groups, 1 or 2 side chains (branched chains) of alkyl groups having 1 to 3 carbon atoms may be bonded to the main chain, or 1 or 2 carbon atoms 1 to 3 side chains (branched chains) of the alkyl group may be bonded. In the case of an aliphatic group having 11 to 13 carbon atoms, the side of the alkyl group having 1 to 3 carbon atoms with respect to the main chain 1 chain (branched chain) may be bonded, or 1 to 3 side chains (branched chains) of an alkyl group having 1 carbon atom may be bonded. In the case of an aliphatic group, one or two side chains (branched chains) of an alkyl group having 1 carbon atom may be bonded to the main chain, or there is no side chain.

  More specifically, the case of long side chain bonding will be described in more detail. “Substantially straight chain” means, for example, an aliphatic group having 12 to 26 carbon atoms and 6 to 10 carbon atoms relative to the main chain. It means that one side chain (branched chain) of the linear alkyl group may be bonded. In the case of an aliphatic group having 8 to 11 carbon atoms, there is no side chain.

  The substantially straight-chain or straight-chain aliphatic group may contain 1 to 3, or 1 or 2 carbon-carbon double bonds or carbon-carbon triple bonds, and may contain one. Also good.

Any carbon in the substantially straight-chain or straight-chain aliphatic group may be replaced with —O—, —SiR ₂ — (R is alkyl having 1 to 4 carbon atoms) or cyclohexanediyl. It may be replaced, may be replaced at one or two places, and may be replaced at one place.

<Substituent for R ^{1 to} R ⁴ >
The “aliphatic group” or “substantially linear or linear aliphatic group having 8 to 26 carbon atoms” may be substituted, and examples of the substituent include alkyl, alkenyl, alkynyl, cycloalkyl , Alkoxy, aryl, heteroaryl or halogen (particularly preferred is fluorine). The number of substituents is, for example, the maximum possible number of substitution, preferably 1 to 3, more preferably 1 to 2, and still more preferably 0 (unsubstituted).

As alkyl, the description of alkyl as a substituent to Ar ^{11 to} Ar ⁴² can be cited. Also, alkenyl and alkynyl include those in which some carbon-carbon single bonds in this alkyl are replaced by carbon-carbon double bonds or carbon-carbon triple bonds. The place to be replaced is not particularly limited, and preferably includes 1 to 3 places, more preferably 1 or 2 places, and still more preferably 1 place.

  Examples of cycloalkyl include cycloalkyl having 3 to 12 carbon atoms. C3-C10 cycloalkyl is preferable, C3-C8 cycloalkyl is more preferable, C3-C6 cycloalkyl is more preferable. Specific examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl, methylcyclohexyl, cyclooctyl, and dimethylcyclohexyl.

  Examples of alkoxy include alkoxy having 1 to 15 carbon atoms. C1-C10 alkoxy is preferable and C1-C4 alkoxy is more preferable. Specific examples of alkoxy include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, s-butoxy, t-butoxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, cycloheptyloxy, octyl Examples thereof include oxy and cyclooctyloxy.

  Examples of the aryl include aryl having 6 to 30 carbon atoms. An aryl having 6 to 24 carbon atoms is preferred, an aryl having 6 to 20 carbon atoms is more preferred, an aryl having 6 to 16 carbon atoms is further preferred, and an aryl having 6 to 12 carbon atoms is particularly preferred.

  Specific aryls include monocyclic aryl phenyl, (o-, m-, p-) tolyl, (2,3-, 2,4-, 2,5-, 2,6-, 3, 4-, 3,5-) xylyl, mesityl, (o-, m-, p-) cumenyl, bicyclic aryl (2-, 3-, 4-) biphenylyl, condensed bicyclic aryl ( 1-, 2-) naphthyl, tricyclic aryl terphenylyl (m-terphenyl-2'-yl, m-terphenyl-4'-yl, m-terphenyl-5'-yl, o-terphenyl) -3′-yl, o-terphenyl-4′-yl, p-terphenyl-2′-yl, m-terphenyl-2-yl, m-terphenyl-3-yl, m-terphenyl- 4-yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o-terfe Acenaphthylene- (1-, 3-) which is ru-4-yl, p-terphenyl-2-yl, p-terphenyl-3-yl, p-terphenyl-4-yl), a fused tricyclic aryl. , 4-, 5-) yl, fluorene- (1-, 2-, 3-, 4-, 9-) yl, phenalen- (1-, 2-) yl, (1-, 2-, 3-, 4-, 9-) phenanthryl, tetracyclic aryl quaterphenylyl (5'-phenyl-m-terphenyl-2-yl, 5'-phenyl-m-terphenyl-3-yl, 5'- Phenyl-m-terphenyl-4-yl, m-quaterphenyl), triphenylene- (1-, 2-) yl which is a fused tetracyclic aryl, pyrene- (1-, 2-, 4-) yl, Naphtacene- (1-, 2-, 5-) yl, perylene which is a fused pentacyclic aryl (1-, 2-, 3-) yl, pentacene - (1-, 2-, 5-, 6-) yl, and the like.

  Examples of heteroaryl include heteroaryl having 2 to 30 carbon atoms. Heteroaryl having 2 to 25 carbon atoms is preferred, heteroaryl having 2 to 20 carbon atoms is more preferred, heteroaryl having 2 to 15 carbon atoms is further preferred, and heteroaryl having 2 to 10 carbon atoms is particularly preferred. Examples of the heteroaryl include heterocycles containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon as ring constituent atoms.

  Specific examples of heteroaryl include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, furazanyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, Isobenzofuranyl, benzo [b] thienyl, indolyl, isoindolyl, 1H-indazolyl, benzoimidazolyl, benzoxazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, purinyl Pteridinyl, carbazolyl, acridinyl, phenoxazinyl, phenothiazinyl, Najiniru, phenoxathiinyl, thianthrenyl, etc. indolizinyl, and the like, thienyl, imidazolyl, pyridyl, such as carbazolyl are preferable.

<Regarding the number of substitution of R ^{1 to} R ⁴ >
1c-4c is respectively independently the integer of 1-5, the integer of 1-4 is preferable, the integer of 1-3 is more preferable, 1 or 2 is further more preferable, and 1 is especially preferable.

<Regarding the Asymmetric Carbon of R ^{1 to} R ⁴ >
The “aliphatic group” or “substantially linear or linear aliphatic group having 8 to 26 carbon atoms” may have an asymmetric carbon. The position of the asymmetric carbon in the group is not particularly limited, and when it has an asymmetric carbon, it preferably has 1 to 3, more preferably 1 or 2, and more preferably one. It is done. In the case of having an asymmetric carbon, the anthracene derivative of the present invention can form a racemate or an optically active form, but the optically active form may increase the self-assembly ability of the anthracene derivative.

<Substitution number of SUB2 and SUB4>
n and m are each independently an integer of 1 to 4, more preferably an integer of 1 to 3, more preferably 1 or 2, and particularly preferably 1. In addition, the substitution position of “SUB2-” may be any of the 1st to 4th positions of anthracene, but is preferably substituted to the 2nd position preferentially. The substitution position of “SUB4-” may be any of the 5th to 8th positions of anthracene, but it is preferable to substitute the 6th position preferentially.

<Self-organization and structure of anthracene derivatives>
The anthracene derivatives of the present invention are self-assembled by placing a suitable number of substituted or unsubstituted, substantially linear or linear aliphatic groups of appropriate chain length at appropriate positions in the molecule. Is possible. Appropriate positions and numbers of aliphatic groups are positions and numbers suitable for self-organization to a distance where the interaction between the aromatic ring parts of the molecule works effectively, and depending on the structure of the anthracene derivative Different. An aliphatic group substituted at an inappropriate position or an excessive number of aliphatic groups restricts the direction of interaction between aromatic rings or weakens the interaction between aromatic rings. Also, the appropriate chain length of the aliphatic group is that self-organization hardly occurs when the aliphatic group is too short, and when the aliphatic group is too long, the effect of self-assembly is diminished by folding of the aliphatic group. That is, since the interaction between the aromatic ring portions of the molecule is weakened, the chain length between them is an appropriate chain length.

<Self-organization and deposition conditions>
The energy required to cause self-organization is covered by molecular collision during vapor deposition or thermal energy applied during or after device fabrication. The molecular collision means that a molecule that has jumped out of a deposition source collides with a substrate or a molecule formed on the substrate. The kinetic energy of the flying molecules is converted into thermal energy by collision, and the thermal energy minus the heat release is used for self-organization. Therefore, the higher the film formation rate, the more heat is stored and the self-organization is promoted. In addition, as the number of carbon atoms in the material molecule increases, the latent heat of sublimation increases, and the thermal energy of the molecules jumping out from the evaporation source also increases, so that self-assembly is promoted. The film forming speed varies depending on the structure of the material molecule, the alkyl chain length, and the like, and is not particularly limited, but is 0.01 nm / second to 20.0 nm / second. The film formation rate is preferably 0.2 nm / second or more, more preferably 0.5 nm / second or more, and further preferably 1 nm / second or more, and the degree of self-assembly is high.

<Self-organization and heating conditions>
Furthermore, when the film formation rate is less than 0.2 nm / second or when the number of carbon atoms of the linear or linear aliphatic group is 8 to 14, when the degree of self-assembly is not sufficient, The degree of self-organization can also be increased by heating within the range of room temperature or higher and lower than the lowest glass transition point (Tg) of materials constituting the element during or after the element fabrication. . When heated at a temperature higher than Tg, undesirable phenomena such as crystallization of a layer that is not a self-organizing material may occur.

  The required heating time varies depending on the length of the linear or linear aliphatic group, the substitution position of the aliphatic group on the aromatic ring, the structure of the aromatic ring, and the film formation rate. Self-assemble in 100 hours. When the heating temperature can be set to 100 ° C. or more and the film formation rate is 1 nm / second or more, the heating time may be short, preferably 1 minute to 30 minutes, and when the heating temperature is low or the film is formed. When the speed is low, it is necessary to lengthen the heating time. As a method of external heating, any of thermal radiation, convection, and heat conduction may be used. Therefore, it can be performed under vacuum or atmospheric pressure regardless of the pressure environment during heating.

  Specific examples of the anthracene derivative represented by the general formula (1) are shown below, but are not limited to the compounds represented by the following formulas (1-1) to (1-989). Among the following compounds, the following formula (1-1) to formula (1-48), formula (1-61) to formula (1-120), formula (1-157) to formula (1-228), formula ( 1-444) to formula (1-462), formula (1-486) to formula (1-497), and formula (1-510) to formula (1-989) are preferred, and the following formula (1- 1) to formula (1-36), formula (1-37), formula (1-43), formula (1-61) to formula (1-72), formula (1-94) to formula (1-98) ), Formula (1-109) to formula (1-120), formula (1-157) to formula (1-189), formula (1-193) to formula (1-201), formula (1-205) Formula (1-228), Formula (1-444) to Formula (1-454), Formula (1-486) to Formula (1-496), Formula (1-510) to Formula (1-520), Formula (1-528)-Formula (1-6) 3), and the compound of formula (1-738) to (1-989) are more preferable.

2. Method for synthesizing compound represented by general formula (1) An anthracene derivative represented by general formula (1) is prepared by a known method using a halogenated aryl derivative and an anthracene derivative boronic acid as starting materials, or a halogenated aryl boronic acid. Starting from a derivative and a halogenated anthracene, they can be synthesized by appropriately combining Suzuki / Miyaura coupling, Kumada / Tamao / Colleu coupling, Negishi coupling, halogenation reaction, or boration reaction. The synthesis scheme is illustrated below.

In the following synthesis scheme, the following four types of substituents substituted with anthracene will be described using abbreviations as follows.
^{_{"(R 1) 1c - (Ar}} 12) 1b - (Ar 11) 1a - " = "SUB1-"
“(R ² ) _2c − (Ar ²² ) _2b − (Ar ²¹ ) _2a −” = “SUB ₂ −”
“(R ³ ) _3c − (Ar ³² ) _3b − (Ar ³¹ ) _3a −” = “SUB ₃ −”
^{_{"(R 4) 4c - (Ar}} 42) 4b - (Ar 41) 4a - " = "SUB4-"
In addition, “M”, “X”, and “—B (OR) ₂ ” in Synthesis Scheme 2 and later are the same as those described in Scheme 1.

  Next, an example of a method for synthesizing the raw material of the aryl group or alkyl group moiety (“SUB1-” to “SUB4-”) to be introduced into the anthracene ring used for the synthesis of the anthracene derivative of the above general formula (1) will be described below. Show. The case of the “SUB1-” group is shown as an example, but other “SUB2-” to “SUB4-” groups can be synthesized in the same manner. Further, in the case of a = 0 and a = b = 0, other alkyl groups and aryl groups can also be synthesized by the method exemplified below.

The reactive functional group of the halide and boronic acid derivative in the Suzuki-Miyaura coupling may be replaced as appropriate, and the functional group involved in these reactions also in the Kumada / Tamao / Coryu coupling and Negishi coupling. May be replaced. Further, when converting to the Grignard reagent, the metal magnesium and the isopropyl grinder reagent may be appropriately replaced. The boronic acid ester may be used as it is, or may be hydrolyzed with an acid and used as a boronic acid. When used as a boronic ester, an alkyl group other than those exemplified above can be used as the alkyl group of the ester moiety. Note that “X” and “—B (OR) ₂ ” in the raw material synthesis method ₂ and later are the same as those described in the raw material synthesis method 1.

Specific examples of the palladium catalyst used in the reaction include tetrakis (triphenylphosphine) palladium (0): Pd (PPh ₃ ) ₄ , bis (triphenylphosphine) palladium (II) dichloride: PdCl ₂ (PPh ₃ ) ₂ , Palladium (II) acetate: Pd (OAc) ₂ , tris (dibenzylideneacetone) dipalladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) dipalladium (0) chloroform complex: Pd ₂ (dba) ₃ · CHCl _3, bis (dibenzylideneacetone) palladium _{(0): Pd (dba)} 2, bis (tri-t- butyl phosphino) palladium _{(0): Pd (t-} Bu 3 P) 2, [1,1 '-Bis (diphenylphosphino) ferrocene] dichloropalladium (II): Pd (d ppf) Cl ₂ , [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) dichloromethane complex (1: 1): Pd (dppf) Cl ₂ .CH ₂ Cl ₂ , PdCl ₂ {P (t _{-Bu) 2 - (p-NMe} 2 -Ph)} 2: (A- ta Phos) 2 PdCl 2, palladium bis (dibenzylideneacetone), [1,3-bis (diphenylphosphino) propane] nickel (II) _{dichloride, PdCl 2 [P (t-} Bu) 2 - (p-NMe 2 -Ph)] 2: (A- ta Phos) 2 PdCl 2 (Pd-132: trademark, manufactured by Johnson Matthey Inc.).

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

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

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

  In addition, the anthracene derivative of the present invention includes those in which at least a part of hydrogen atoms are substituted with deuterium. Such a derivative can be obtained by using a raw material in which a desired portion is deuterated. It can be synthesized in the same manner as above.

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

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

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

  Not all of the above layers are necessary, and the minimum structural unit is composed of the anode 102, the light emitting layer 105, and the cathode 108, and the hole injection layer 103, the hole transport layer 104, the electron transport layer 106, and the electron injection. The layer 107 is an arbitrarily provided layer. Moreover, each said layer may consist of a single layer, respectively, and may consist of multiple layers.

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

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

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

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

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

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

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

As a material for forming the hole injection layer 103 and the hole transport layer 104, an anthracene derivative represented by the above general formula (1) can be used. In addition, among photoconductive materials, compounds conventionally used as hole charge transport materials, p-type semiconductors, and known materials used in hole injection layers and hole transport layers of organic electroluminescence devices Any one can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis (N-arylcarbazole) or bis (N-alkylcarbazole), triarylamine derivatives (aromatic tertiary class). Polymer having amino in main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4 , 4′-diaminobiphenyl, N, N′-diphenyl-N, N′-dinaphthyl-4,4′-diaminobiphenyl, N, N′-diphenyl-N, N′-di (3-methylphenyl) -4 , 4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl-1,1′-diamine, ^4, N ^{4 '-} diphenyl ^{-N 4,} N ^4' - bis (9-phenyl -9H- carbazol-3-yl) - [1,1'-biphenyl] ^{-4,4'-diamine, N} 4, N ^4, N ^{4 ',} N ^4' - tetramethyl [1,1'-biphenyl] -4-yl) - [1,1'-biphenyl] -4,4'-diamine, 4,4 ', 4 "- tris (Triphenylamine derivatives such as (3-methylphenyl (phenyl) amino) triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives And thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (for example, 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7, 0,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonates, styrene derivatives, polyvinylcarbazole, polysilanes, etc. having the above monomers in the side chain are preferred, but light emission There is no particular limitation as long as it is a compound that can form a thin film necessary for manufacturing the device, inject holes from the anode, and further transport holes.

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

<Light emitting layer in organic electroluminescent element>
The light emitting layer 105 emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 105 may be a compound that emits light by being excited by recombination of holes and electrons (a light-emitting compound), can form a stable thin film shape, and is in a solid state It is preferable that the compound exhibits a strong light emission (fluorescence) efficiency. In the present invention, an anthracene derivative represented by the general formula (1) can be used as a material for the light emitting layer.

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

  The amount of the host material used varies depending on the type of the host material, and may be determined according to the characteristics of the host material. The amount of the host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, and still more preferably 90 to 99.9% by weight of the entire light emitting layer material. It is. The anthracene derivative represented by the general formula (1) can also be used as a host material.

  The amount of dopant material used depends on the type of dopant material, and may be determined according to the characteristics of the dopant material. The standard of the amount of dopant used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and further preferably 0.1 to 10% by weight of the entire material for the light emitting layer. is there. The above range is preferable in that, for example, the concentration quenching phenomenon can be prevented. The anthracene derivative represented by the general formula (1) can also be used as a dopant material.

  Host materials that can be used in combination with the anthracene derivative represented by the general formula (1) include condensed ring derivatives such as anthracene and pyrene, bisstyrylanthracene derivatives and distyrylbenzene derivatives that have been known as light emitters. And bisstyryl derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, fluorene derivatives, benzofluorene derivatives, and the like.

  Moreover, it does not specifically limit as a dopant material which can be used together with the anthracene derivative represented by the said General formula (1), A well-known compound can be used and various according to desired luminescent color. You can choose from various materials. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopylene, dibenzopyrene, rubrene and chrysene, benzoxazole derivatives, benzothiazole derivatives, benzimidazole derivatives, benzotriazole derivatives, oxazoles Derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, distyrylbenzene derivatives, etc. (Japanese Patent Laid-Open No. 1-245087), bisstyrylarylene derivatives (Japanese Patent Laid-Open No. 2-24727) Gazette), diazaindacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimesitylisobenzofuran, di (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, phenylisobenzofuran, etc. Isobenzofuran derivatives, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, 7-acetoxycoumarin derivatives, 3-benzothiazolylcoumarin derivatives, 3 -Benzimidazolyl coumarin derivatives, coumarin derivatives such as 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, polymethine derivatives, Nin derivatives, oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyril derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1, Examples include 2,5-thiadiazolopyrene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, violanthrone derivatives, phenazine derivatives, acridone derivatives, deazaflavin derivatives, fluorene derivatives, and benzofluorene derivatives.

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

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

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

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

  Among the dopant materials described above, amines having a stilbene structure, perylene derivatives, borane derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives or pyrene derivatives are particularly preferable.

当該式中、Ａｒ^１は炭素数６〜３０のアリールに由来するｍ価の基であり、Ａｒ^２およびＡｒ^３は、それぞれ独立して炭素数６〜３０のアリールであるが、Ａｒ^１〜Ａｒ^３の少なくとも１つはスチルベン構造を有し、Ａｒ^１〜Ａｒ^３は置換されていてもよく、そして、ｍは１〜４の整数である。 The amine having a stilbene structure is represented by the following formula, for example.

In the formula, Ar ¹ is an m-valent group derived from aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, Ar ^{1 to} Ar ^At least one of ³ has a stilbene structure, Ar ^{1 to} Ar ³ may be substituted, and m is an integer of 1 to 4.

当該式中、Ａｒ^２およびＡｒ^３は、それぞれ独立して炭素数６〜３０のアリールであり、Ａｒ^２およびＡｒ^３は置換されていてもよい。 The amine having a stilbene structure is more preferably a diaminostilbene represented by the following formula.

In the formula, Ar ² and Ar ³ are each independently aryl having 6 to 30 carbon atoms, and Ar ² and Ar ³ may be substituted.

  Specific examples of the aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorene, phenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, stilbene, distyrylbenzene, distyrylbiphenyl, and distyryl. Examples include fluorene.

Specific examples of amines having a stilbene structure include N, N, N ′, N′-tetra (4-biphenylyl) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (1-naphthyl) ) -4,4′-diaminostilbene, N, N, N ′, N′-tetra (2-naphthyl) -4,4′-diaminostilbene, N, N′-di (2-naphthyl) -N, N '-Diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) -N, N'-diphenyl-4,4'-diaminostilbene, 4,4'-bis [4 "-bis (Diphenylamino) styryl] -biphenyl, 1,4-bis [4′-bis (diphenylamino) styryl] -benzene, 2,7-bis [4′-bis (diphenylamino) styryl] -9,9-dimethyl Fluorene, 4,4′-bis (9-ethyl-3-cal And bazovinylene) -biphenyl and 4,4′-bis (9-phenyl-3-carbazovinylene) -biphenyl.
Moreover, you may use the amine which has a stilbene structure described in Unexamined-Japanese-Patent No. 2003-347056, Unexamined-Japanese-Patent No. 2001-307884, etc.

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

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

当該式中、Ａｒ^４は炭素数６〜３０のアリールに由来するｎ価の基であり、Ａｒ^５およびＡｒ^６はそれぞれ独立して炭素数６〜３０のアリールであり、Ａｒ^４〜Ａｒ^６は置換されていてもよく、そして、ｎは１〜４の整数である。 The aromatic amine derivative is represented by the following formula, for example.

In the formula, Ar ⁴ is an n-valent group derived from aryl having 6 to 30 carbon atoms, Ar ⁵ and Ar ⁶ are each independently aryl having 6 to 30 carbon atoms, and Ar ^{4 to} Ar ⁶ are It may be substituted and n is an integer from 1 to 4.

In particular, Ar ⁴ is a divalent group derived from anthracene, chrysene, fluorene, benzofluorene or pyrene, Ar ⁵ and Ar ⁶ are each independently an aryl having 6 to 30 carbon atoms, and Ar ^{4 to} Ar ⁶ Are more preferably aromatic amine derivatives wherein n is 2 and n is 2.

  Specific examples of the aryl having 6 to 30 carbon atoms include benzene, naphthalene, acenaphthylene, fluorenephenalene, phenanthrene, anthracene, fluoranthene, triphenylene, pyrene, chrysene, naphthacene, perylene, and pentacene.

  Examples of the aromatic amine derivative include chrysene-based compounds such as N, N, N ′, N′-tetraphenylchrysene-6,12-diamine, N, N, N ′, N′-tetra (p-tolyl). Chrysene-6,12-diamine, N, N, N ′, N′-tetra (m-tolyl) chrysene-6,12-diamine, N, N, N ′, N′-tetrakis (4-isopropylphenyl) chrysene -6,12-diamine, N, N, N ', N'-tetra (naphthalen-2-yl) chrysene-6,12-diamine, N, N'-diphenyl-N, N'-di (p-tolyl) ) Chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis ( 4-ethylphenyl) chrysene-6 2-diamine, N, N′-diphenyl-N, N′-bis (4-isopropylphenyl) chrysene-6,12-diamine, N, N′-diphenyl-N, N′-bis (4-t-butyl) Phenyl) chrysene-6,12-diamine, N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) chrysene-6,12-diamine, and the like.

  Examples of the pyrene-based compound include N, N, N ′, N′-tetraphenylpyrene-1,6-diamine, N, N, N ′, N′-tetra (p-tolyl) pyrene-1,6. -Diamine, N, N, N ', N'-tetra (m-tolyl) pyrene-1,6-diamine, N, N, N', N'-tetrakis (4-isopropylphenyl) pyrene-1,6- Diamine, N, N, N ′, N′-tetrakis (3,4-dimethylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-di (p-tolyl) pyrene-1 , 6-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-bis (4-ethylphenyl) ) Pyrene-1,6-diamine, N, N'-diphenyl-N, N'- Su (4-isopropylphenyl) pyrene-1,6-diamine, N, N′-diphenyl-N, N′-bis (4-t-butylphenyl) pyrene-1,6-diamine, N, N′-bis (4-Isopropylphenyl) -N, N′-di (p-tolyl) pyrene-1,6-diamine, N, N, N ′, N′-tetrakis (3,4-dimethylphenyl) -3,8- And diphenylpyrene-1,6-diamine.

  Examples of the anthracene system include N, N, N, N-tetraphenylanthracene-9,10-diamine, N, N, N ′, N′-tetra (p-tolyl) anthracene-9,10-diamine. N, N, N ′, N′-tetra (m-tolyl) anthracene-9,10-diamine, N, N, N ′, N′-tetrakis (4-isopropylphenyl) anthracene-9,10-diamine, N, N′-diphenyl-N, N′-di (p-tolyl) anthracene-9,10-diamine, N, N′-diphenyl-N, N′-di (m-tolyl) anthracene-9,10- Diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4-ethylphenyl) anthrace -9,10-diamine, N, N'-diphenyl-N, N'-bis (4-isopropylphenyl) anthracene-9,10-diamine, N, N'-diphenyl-N, N'-bis (4- t-butylphenyl) anthracene-9,10-diamine, N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) anthracene-9,10-diamine, 2,6-di -T-butyl-N, N, N ', N'-tetra (p-tolyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-diphenyl-N, N' -Bis (4-isopropylphenyl) anthracene-9,10-diamine, 2,6-di-t-butyl-N, N'-bis (4-isopropylphenyl) -N, N'-di (p-tolyl) Anthracene-9,10-diamy 2,6-dicyclohexyl-N, N′-bis (4-isopropylphenyl) -N, N′-di (p-tolyl) anthracene-9,10-diamine, 2,6-dicyclohexyl-N, N′- Bis (4-isopropylphenyl) -N, N′-bis (4-t-butylphenyl) anthracene-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- And 9- (6-diphenylamino-2-naphthyl) anthracene.

Examples of pyrene-based compounds include N, N, N, N-tetraphenyl-1,8-pyrene-1,6-diamine and N-biphenyl-4-yl-N-biphenyl-1,8-pyrene-1. , ^6-diamine, N 1, ^{N 6} - diphenyl ^-N 1, ^{N 6} - bis - (4-trimethylsilanyl - phenyl)-1H, such 8H- 1,6-diamine.

Other examples include [4- (4-diphenylamino-phenyl) naphthalen-1-yl] -diphenylamine, [6- (4-diphenylamino-phenyl) naphthalen-2-yl] -diphenylamine, 4,4 ′. -Bis [4-diphenylaminonaphthalen-1-yl] biphenyl, 4,4'-bis [6-diphenylaminonaphthalen-2-yl] biphenyl, 4,4 "-bis [4-diphenylaminonaphthalen-1-yl] ] -P-terphenyl, 4,4 "-bis [6-diphenylaminonaphthalen-2-yl] -p-terphenyl, and the like.
Moreover, you may use the aromatic amine derivative described in Unexamined-Japanese-Patent No. 2006-156888.

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

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

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

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

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

  As a material (electron transport material) for forming the electron transport layer 106 or the electron injection layer 107, an anthracene derivative represented by the general formula (1) can be used. In addition, it can be arbitrarily selected from compounds conventionally used as electron transport compounds in photoconductive materials and known compounds used in electron injection layers and electron transport layers of organic electroluminescent devices. .

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

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

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

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

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

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

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

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

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

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

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

  Specific examples of the pyridine derivative include 2,5-bis (2,2′-pyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5-bis (2,2′- Pyridin-6-yl) -1,1-dimethyl-3,4-dimesitylsilole, 2,5-bis (2,2′-pyridin-5-yl) -1,1-dimethyl-3,4 Diphenylsilole, 2,5-bis (2,2′-pyridin-5-yl) -1,1-dimethyl-3,4-dimesitylsilole, 9,10-di (2,2′-pyridine-6) -Yl) anthracene, 9,10-di (2,2'-pyridin-5-yl) anthracene, 9,10-di (2,3'-pyridin-6-yl) anthracene, 9,10-di (2 , 3′-Pyridin-5-yl) anthracene, 9,10-di (2,3′-pyridine) -Yl) -2-phenylanthracene, 9,10-di (2,3'-pyridin-5-yl) -2-phenylanthracene, 9,10-di (2,2'-pyridin-6-yl)- 2-phenylanthracene, 9,10-di (2,2′-pyridin-5-yl) -2-phenylanthracene, 9,10-di (2,4′-pyridin-6-yl) -2-phenylanthracene 9,10-di (2,4′-pyridin-5-yl) -2-phenylanthracene, 9,10-di (3,4′-pyridin-6-yl) -2-phenylanthracene, 9,10 -Di (3,4'-pyridin-5-yl) -2-phenylanthracene, 3,4-diphenyl-2,5-di (2,2'-pyridin-6-yl) thiophene, 3,4-diphenyl -2,5-di (2,3'-pyridine 5-yl) thiophene, 6'6 "- di (2-pyridyl) 2,2 ': 4', 4": 2 ", 2" '- like quaterphenyl pyridine.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

<Synthesis of Intermediates of Compounds Used in Examples and Comparative Examples>
[Synthesis Example 1] (Synthesis of 2- (anthracen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
2-bromoanthracene (17.0 g), 4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2,2′-bi (1,3,2-dioxaborolane) (25. 2 g), potassium acetate (7.14 g), anisole (150 ml), bis (dibenzylideneacetone) palladium (0) (1.14 g), tricyclohexylphosphine (1.11 g) were placed in a flask under a nitrogen atmosphere. Stir at 130 ° C. for 1.5 hours. The reaction solution is cooled and then filtered, and heptane is added to the filtrate concentrated precipitate, followed by further filtration. The obtained solid is washed with heptane and then vacuum-dried to give 2- (anthracen-2-yl) -4, 4,5,5-tetramethyl-1,3,2-dioxaborolane (17.9 g) was obtained.

[Synthesis Example 2] (Synthesis of 2- (4-bromophenyl) anthracene)
2- (anthracen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (20 g) synthesized by the method of Synthesis Example 1 and 1-bromo-4-iodobenzene (21 .6 g), tetrakis (triphenylphosphine) palladium (0) (482 mg), tripotassium phosphate (27.9 g), toluene (200 ml), t-butanol (20 ml) and water (4 ml) were placed in a flask, The mixture was stirred at reflux temperature for 6 hours under a nitrogen atmosphere. After cooling, water was added, and only the organic solvent was distilled off under reduced pressure. The precipitate was collected by filtration, washed successively with water, methanol and heptane, and then dried in vacuo to give 2- (4-bromophenyl) anthracene (13.0 g).

[Synthesis Example 3] (Synthesis of 2- (4-dodecylphenyl) anthracene)
2- (4-Bromophenyl) anthracene (13.0 g), [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride (303 mg), and cyclopentyl methyl ether (303 mg) synthesized by the method of Synthesis Example 2 60 ml) was placed in a flask, cooled with ice water in a nitrogen atmosphere, and dodecylmagnesium bromide was added dropwise over 15 minutes so that the internal temperature did not exceed 25 ° C. Subsequently, after heating up to room temperature, it stirred at room temperature for 3 hours. After cooling with ice water again, water was slowly added dropwise to stop the reaction, then neutralized with 1N hydrochloric acid, heptane was added, and the precipitate was filtered. The obtained solid was washed successively with water, methanol and heptane and then vacuum dried to obtain 2- (4-dodecylphenyl) anthracene (16.7 g).

[Synthesis Example 4] (Synthesis of 9,10-dibromo-2- (4-dodecylphenyl) anthracene)
2- (4-dodecylphenyl) anthracene (16.7 g) and acetonitrile (34 ml) synthesized by the method of Synthetic Example 3 were put in a flask, and N-bromosuccinimide (15.5 g) was added little by little, followed by room temperature. For 21 hours. A small amount of sodium bisulfite and sodium hydrogen carbonate were added next to water, extracted with toluene, washed with water, dried over anhydrous sodium sulfate, and filtered. The solid obtained by concentrating the filtrate to dryness was washed with heptane and then vacuum-dried to obtain 9,10-dibromo-2- (4-dodecylphenyl) anthracene (9.61 g).

[Synthesis Example 5] (2,2 ′-(2- (4-dodecylphenyl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) Synthesis)
9,10-Dibromo-2- (4-dodecylphenyl) anthracene (9.61 g), 4,4,5,5-tetramethyl-1,3,2-dioxaborolane (10.10) synthesized by the method of Synthesis Example 4. 1 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane complex (1: 1) (242 mg), potassium acetate (6.50 g), toluene (48 ml), dimethyl sulfoxide (9 6 ml) was placed in a flask and stirred at reflux temperature for 9 hours under a nitrogen atmosphere. After completion of the heating, the reaction solution was cooled to room temperature, and water was added for liquid separation. The organic layer was concentrated under reduced pressure and then purified by silica gel column chromatography (toluene) to obtain 2,2 ′-(2- (4-dodecylphenyl) anthracene-9,10-diyl) bis (4,4,5 , 5-tetramethyl-1,3,2-dioxaborolane) (2.0 g).

[Synthesis Example 6] (Synthesis of 9,10-dibromo-2-chloroanthracene)
2-Chloroanthracene (40.9 g) and chloroform (490 ml) were placed in a flask, and after ice cooling, bromine was added dropwise over 15 minutes so that the internal temperature did not exceed 10 ° C. Next, after stirring at room temperature for 30 minutes, an aqueous sodium hydrogen sulfite solution was added dropwise to treat excess bromine, and further neutralized by adding sodium hydrogen carbonate. Heptane (500 ml) was added and filtered, and the resulting solid was washed with water and then ethanol and then vacuum dried to obtain 9,10-dibromo-2-chloroanthracene (71 g).

[Synthesis Example 7] (Synthesis of 2,2 ′-(2-chloroanthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane))
9,10-Dibromo-2-chloroanthracene (35 g), 4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2,2′-bi synthesized by the method of Synthesis Example 6 (1,3,2-dioxaborolane) (52.8 g), potassium acetate (37.1 g), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane complex (1: 1) ( 2.07 g) and anisole (350 ml) were placed in a flask and heated and stirred at 120 ° C. for 2 hours under a nitrogen atmosphere. The reaction solution was cooled and filtered through celite, and then the filtrate was concentrated. The concentrated precipitate was filtered with heptane, washed with heptane, and 2,2 ′-(2-chloroanthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3). , 2-dioxaborolane) (20.3 g).

[Synthesis Example 8] (Synthesis of 4,4 ′-((2-chloroanthracene-9,10-diyl) bis (3,1-phenylene)) dipyridine)
2,2 ′-(2-Chloroanthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (57.5 g) synthesized by the method of Synthesis Example 7 ), 4- (3-bromophenyl) pyridine (61.0 g), tetrakis (triphenylphosphine) palladium (0) (7.16 g), tripotassium phosphate (105 g), toluene (250 ml), t-butanol ( 50 ml) and water (10 ml) were placed in a flask and stirred at reflux temperature for 6 hours under a nitrogen atmosphere. The reaction mixture was cooled and filtered through celite, and then the filtrate was concentrated. The concentrate was purified by silica gel column chromatography (ethyl acetate), then washed with methanol and dried in vacuo to give 4,4 ′-((2-chloroanthracene-9,10-diyl) bis (3,1-phenylene). )) Dipyridine (25.0 g) was obtained.

[Synthesis Example 9] (Synthesis of 4,4 ′-((2-chloroanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine)
2,2 ′-(2-Chloroanthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) (10.0 g) synthesized by the method of Synthesis Example 7 ), 4- (4-bromophenyl) pyridine (11.1 g), tetrakis (triphenylphosphine) palladium (0) (394 mg), tripotassium phosphate (13.7 g), toluene (100 ml), t-butanol ( 10 ml) and water (2 ml) were placed in a flask and stirred at reflux temperature for 2 hours under a nitrogen atmosphere. After cooling the reaction solution, water is added, and the precipitated solid is collected by filtration, washed successively with water, methanol, heptane, and toluene, and then dried in vacuo to give 4,4 ′-((2-chloroanthracene-9, 10-Diyl) bis (4,1-phenylene)) dipyridine (7.16 g) was obtained.

[Synthesis Example 10] (Synthesis of (4-dodecylphenyl) boronic acid)
Magnesium (3.3 g) and tetrahydrofuran (20 ml) are placed in a flask, and a solution of 1-bromo-4-dodecylbenzene (40.1 g) in tetrahydrofuran (100 ml) is slowly added dropwise at a rate to maintain reflux. 4-Dodecylphenyl) magnesium bromide was prepared. This was cooled in an ice-water bath and trimethyl borate (15.4 g) was slowly added dropwise. After stirring at room temperature for 1 hour, water and then concentrated hydrochloric acid (16 ml) were added and stirred for 30 minutes. The mixture was extracted with ethyl acetate, washed with water, dried over anhydrous sodium sulfate, and concentrated to give (4-dodecylphenyl) boronic acid (32 g).

[Synthesis Example 11] (Synthesis of 9- (4-dodecylphenyl) anthracene)
9-bromoanthracene (20.5 g), (4-dodecylphenyl) boronic acid (29 g) synthesized by the method of Synthesis Example 10, bis (di-t-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II ) (566 mg), tripotassium phosphate (33.9 g), toluene (290 ml), t-butanol (29 ml) and water (2.9 ml) were placed in a flask and stirred at reflux temperature for 2 hours under a nitrogen atmosphere. . The reaction solution was cooled and then filtered through silica gel, and the filtrate was concentrated. After dissolving in heptane and filtering to remove insoluble matter, the filtrate concentrate was recrystallized twice from heptane to give 9- (4-dodecylphenyl) anthracene (25.8 g).

[Synthesis Example 12] (Synthesis of 9-bromo-10- (4-dodecylphenyl) anthracene)
9- (4-dodecylphenyl) anthracene (17.7 g) synthesized by the method of Synthesis Example 11 and N, N-dimethylformamide (90 ml) were placed in a flask, and N-bromosuccinimide (8.2 g) was added at room temperature. It was added little by little. Next, 36 ml of chloroform was added and stirred at room temperature for 4 hours. Water was added, a small amount of sodium hydrogen sulfite and then sodium hydrogen carbonate were added, and then the reaction solution was heated under reduced pressure to distill off chloroform. The solid obtained by filtering the precipitate was washed with water, ethanol and heptane in this order, vacuum-dried and then reprecipitated from toluene / heptane to give 9-bromo-10- (4-dodecylphenyl) anthracene (10 .4 g) was obtained.

[Synthesis Example 13] (Synthesis of 2- (10- (4-dodecylphenyl) anthracen-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane)
9-Bromo-10- (4-dodecylphenyl) anthracene (10.4 g), 4,4,4 ′, 4 ′, 5,5,5 ′, 5′-octamethyl-2 synthesized by the method of Synthesis Example 12 , 2'-bi (1,3,2-dioxaborolane) (7.8 g), potassium acetate (4.2 g), bis (dibenzylideneacetone) palladium (0) (596 mg), 20% toluene solution of tricyclohexylphosphine (3.4 ml) and anisole (38 ml) were placed in a flask and stirred at reflux temperature for 3 hours under a nitrogen atmosphere. The reaction solution was suction filtered through celite, and the filtrate was concentrated and purified by silica gel column chromatography (heptane / toluene = 1/1 (volume ratio)) to give 2- (10- (4-dodecylphenyl) anthracene- 9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (8.55 g) was obtained.

<Synthesis of compounds used in Examples>
[Synthesis Example 14] (Synthesis of Compound (1-1))

2,2 ′-(2- (4-dodecylphenyl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane synthesized by the method of Synthesis Example 5 ) (2.0 g), 4- (4-bromophenyl) pyridine (1.53 g), tetrakis (triphenylphosphine) palladium (0) (54.3 mg), tripotassium phosphate (2.52 g), 1, 2,4-Trimethylbenzene (20 ml), t-butanol (2 ml) and water (0.4 ml) were placed in a flask and stirred at reflux temperature for 6 hours under a nitrogen atmosphere. After completion of heating, the reaction solution was cooled to room temperature and water was added. The precipitated solid was extracted with hot toluene, concentrated under reduced pressure, filtered by adding heptane. The obtained solid was recrystallized from toluene, vacuum-dried, and purified by sublimation on the order of 10 ⁻⁴ Pa at 330 ° C. to give 4,4 ′-((2- (4-dodecylphenyl) anthracene-9, 10-Diyl) bis (4,1-phenylene)) dipyridine (1.08 g) was obtained. The Tg of this compound was not detected.

The structure of the compound obtained by NMR measurement and MS spectrum was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 0.87 (t, 3H, J = 6.6 Hz), 1.24-1.30 (m, 18H), 1.57-1.62 (m, 2H) ), 2.60 (t, 2H, J = 7.8 Hz), 7.21-7.22 (m, 2H), 7.37-7.39 (m, 2H), 7.47-7.48. (M, 2H), 7.64-7.66 (m, 5H), 7.69-7.70 (m, 4H), 7.73-7.76 (m, 2H), 7.81-7 .83 (m, 1H), 7.91-7.93 (m, 5H), 8.75-8.77 (m, 4H).
LC / MS (m / e); 729.8 (M + 1), 730.7, 731.7, 732.7

[Synthesis Example 15] (Synthesis of Compound (1-61))

2,2 ′-(2- (4-octylphenyl) anthracene-9,10-diyl) bis (4,4,5,5-tetra) synthesized by replacing the dodecyl group in Synthesis Examples 3 to 5 with an octyl group, respectively. Methyl-1,3,2-dioxaborolane) (2.4 g), 4- (4-bromophenyl) pyridine (2.18 g), tetrakis (triphenylphosphine) palladium (0) (448 mg), tripotassium phosphate ( 2.47 g), 1,2,4-trimethylbenzene (24 ml), t-butanol (2.4 ml) and water (0.48 ml) were placed in a flask and stirred at reflux temperature for 6 hours under a nitrogen atmosphere. After completion of heating, the reaction solution was cooled to room temperature and water was added. The precipitated solid was extracted with hot toluene, concentrated under reduced pressure, methanol was added, and the mixture was filtered. After reprecipitation of the obtained solid from toluene / methanol was repeated and vacuum-dried, it was purified by sublimation on the order of 10 ⁻³ Pa and 360 ° C. to obtain 4,4 ′-((2- (4-octylphenyl) Anthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine (546 mg) was obtained. The Tg of this compound was not detected.

The structure of the obtained compound was confirmed by NMR measurement and MS spectrum.
¹ H-NMR (CDCl ₃ ): δ = 0.86 (t, 3H, J = 6.9 Hz), 1.25-1.34 (m, 10H), 1.58-1.64 (m, 2H) ), 2.61 (t, 2H, J = 7.8 Hz), 7.21-7.25 (m, 2H), 7.37-7.39 (m, 2H), 7.47-7.48. (M, 2H), 7.64-7.66 (m, 5H), 7.69-7.70 (m, 4H), 7.73-7.76 (m, 2H), 7.81-7 .82 (m, 1H), 7.91-7.93 (m, 5H), 8.75-8.77 (m, 4H).
LC / MS (m / e); 673.8 (M + 1), 674.6, 675.6, 676.6

[Synthesis Example 16] Synthesis of (Compound 1-534)

2,2 ′-(2- (2-octylphenyl) anthracene-9,10-diyl) bis (4,4,5,5-tetramethyl-1,3,2) synthesized in the same manner as in Synthesis Example 5 -Dioxaborolane (1.39 g), 4- (4-bromophenyl) pyridine (1.16 g), tetrakis (triphenylphosphine) palladium (0) (41 mg), tripotassium phosphate (1.43 g), 1, 2,4-Trimethylbenzene (14 ml), t-butanol (1.4 ml) and water (0.28 ml) were placed in a flask and stirred at reflux temperature for 2 hours under a nitrogen atmosphere. After completion of heating, the reaction solution was cooled to room temperature and water was added. The precipitated solid was extracted with hot toluene, concentrated under reduced pressure, heptane was added, and the mixture was collected by filtration and washed with ethanol. After reprecipitation of the obtained solid from toluene / ethanol was repeated and vacuum-dried, it was purified by sublimation on the order of 10 ⁻³ Pa at 320 ° C. Anthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine (299 mg) was obtained. The Tg of this compound was not detected.

The structure of the obtained compound was confirmed by NMR measurement and MS spectrum.
¹ H-NMR (CDCl ₃ ): δ = 0.78 (t, 3H, J = 7.0 Hz), 1.11-1.18 (m, 10H), 1.37-1.42 (m, 2H) ), 2.54 (t, 2H, J = 7.9 Hz), 7.19-7.23 (m, 2H), 7.25-7.29 (m, 2H), 7.36-7.40. (M, 3H), 7.61-7.65 (m, 4H), 7.67-7.70 (m, 5H), 7.72-7.80 (m, 3H), 7.85-7 .94 (m, 4H), 8.72-8.77 (m, 4H).
LC / MS (m / e); 673.7 (M + 1), 674.6, 675.6, 676.6

[Synthesis Example 17] Synthesis of (Compound 1-43)

4,4 ′-((2-chloroanthracene-9,10-diyl) bis (3,1-phenylene)) dipyridine (4.0 g), [1,3-bis (diphenyl) synthesized by the method of Synthesis Example 8 Phosphino) propane] nickel (II) dichloride (125 mg) and cyclopentyl methyl ether (20 ml) were placed in a flask, and a 0.77 M tetrahydrofuran solution (20 ml) of dodecylmagnesium bromide was added dropwise over 10 minutes under a nitrogen atmosphere. After stirring at room temperature for 1 hour, the mixture was stirred at reflux temperature for 2 hours. The reaction solution was cooled to room temperature, water and toluene were added for liquid separation, and the organic layer was concentrated. The obtained concentrate was purified by silica gel column chromatography (ethyl acetate) and vacuum-dried at 200 ° C., and then purified by sublimation at a level of 10 ⁻³ Pa at 320 ° C. to give 4,4 ′-((2-dodecyl). Anthracene-9,10-diyl) bis (3,1-phenylene)) dipyridine (2.59 g) was obtained. The Tg of this compound was not detected.

The structure of the obtained compound was confirmed by NMR measurement and MS spectrum.
¹ H-NMR (CDCl ₃ ): δ = 0.86 (t, 3H, J = 7.0 Hz), 1.21-1.28 (m, 18H), 1.55-1.61 (m, 2H) ), 2.65 (t, 2H, J = 7.7 Hz), 7.24-7.26 (m, 1H), 7.32-7.36 (m, 2H), 7.45 (s, 1H) ), 7.57-7.62 (m, 6H), 7.66-7.80 (m, 7H), 7.84-7.88 (m, 2H), 8.66-8.68 (m , 4H).
LC / MS (m / e); 653.7 (M + 1), 654.6, 655.6, 656.6

[Synthesis Example 18] Synthesis of (Compound 1-535)

4,4 ′-((2-Chloroanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine (2.0 g) synthesized by the method of Synthesis Example 9, 4-tetradecylphenylboronic acid ( 1.35 g), tripotassium phosphate (1.23 g), bis (di-t-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) (28 mg), toluene (20 ml), t-butanol (2 ml) ) And water (0.4 ml) were placed in a flask and stirred at reflux temperature for 16 hours under a nitrogen atmosphere. Water was added to the reaction solution, hot toluene was added to perform extraction and separation, and the organic layer was concentrated. The obtained solid was purified by silica gel column chromatography (toluene / ethyl acetate / methanol), recrystallized from toluene, vacuum-dried at 200 ° C., and sublimated and purified at 350 ° C. on the order of 10 ⁻³ Pa. , 4 ′-((2- (4-tetradecylphenyl) anthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine (257 mg) was obtained. The Tg of this compound was not detected.

The structure of the obtained compound was confirmed by NMR measurement and MS spectrum.
¹ H-NMR (CDCl ₃ ): δ = 0.87 (t, 3H, J = 7.0 Hz), 1.24-1.30 (m, 22H), 1.57-1.62 (m, 2H) ), 2.60 (t, 2H, J = 7.8 Hz), 7.22 (d, 2H, J = 8.2 Hz), 7.37-7.39 (m, 2H), 7.47 (d , 2H, J = 8.2 Hz), 7.62-7.71 (m, 9H), 7.73-7.76 (m, 2H), 7.82 (d, 1H, J = 9.1 Hz) , 7.91-7.94 (m, 5H), 8.75-8.77 (m, 4H).
LC / MS (m / e); 757.7 (M + 1), 758.6, 759.6, 760.7

[Synthesis Example 19] Synthesis of (Compound 1-7)

4,4 ′-((2-Chloroanthracene-9,10-diyl) bis (3,1-phenylene)) dipyridine (2.0 g) synthesized by the method of Synthesis Example 8, 4-dodecylphenylboronic acid (2 .24 g), bis (di-t-butyl (4-dimethylaminophenyl) phosphine) dichloropalladium (II) (82 mg), tripotassium phosphate (1.64 g), toluene (20 ml), t-butanol (2 ml) , And water (0.2 ml) were placed in a flask and stirred at reflux temperature for 4 hours under a nitrogen atmosphere. The reaction solution was filtered through a silica gel short column, and the filtrate was concentrated to dryness. The obtained solid was washed with Solmix and heptane, vacuum-dried at 200 ° C., and purified by sublimation at about 10 ⁻³ Pa at 350 ° C. to give 4,4 ′-((2- (4-dodecylphenyl). ) Anthracene-9,10-diyl) bis (3,1-phenylene)) dipyridine was obtained (71 mg). The Tg of this compound was not detected.

The structure of the obtained compound was confirmed by NMR measurement and MS spectrum.
¹ H-NMR (CDCl ₃ ): δ = 0.88 (t, 3H, J = 6.9 Hz), 1.26-1.34 (m, 18H), 1.62-1.67 (m, 2H) ), 2.65 (t, 2H, J = 7.8 Hz), 7.20-7.91 (m, 23H), 8.67-8.69 (m, 4H).
LC / MS (m / e); 729.7 (M + 1), 730.6, 731.5

[Synthesis Example 20] Synthesis of (Compound 1-37)

4,4 ′-((2-chloroanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine (1.5 g) synthesized by the method of Synthesis Example 9 [1,3-bis (diphenyl) Phosphino) propane] nickel (II) dichloride (47 mg) and cyclopentyl methyl ether (6 ml) were placed in a flask, and 0.96 M tetrahydrofuran solution (6 ml) of dodecylmagnesium bromide was added dropwise over 10 minutes under a nitrogen atmosphere. And stirred at room temperature for 2 hours. The reaction was cooled to room temperature, water was added and the solid was filtered. The obtained solid was dissolved in toluene, insoluble matter was removed by filtration, this was concentrated, recrystallized from toluene, vacuum-dried at 200 ° C., and then purified by sublimation at 10 ⁻³ Pa level at 330 ° C. Thus, 4,4 ′-((2-dodecylanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine (0.18 g) was obtained. The Tg of this compound was not detected.

The structure of the obtained compound was confirmed by NMR measurement and MS spectrum.
¹ H-NMR (CDCl ₃ ): δ = 0.86 (t, 3H, J = 7.0 Hz), 1.22-1.28 (m, 18H), 1.56-1.61 (m, 2H) ), 2.66 (t, 2H, J = 7.7 Hz), 7.25 (d, 1H, J = 7.8 Hz), 7.33-7.37 (m, 2H), 7.46 (s) , 1H), 7.607.64 (m, 4H), 7.67-7.76 (m, 7H), 7.89-7.93 (m, 4H), 8.75-9.77 (m). , 4H).
LC / MS (m / e); 653.8 (M + 1), 654.7, 655.7, 656.8.

[Synthesis Example 21] Synthesis of (Compound 1-690)

2- (10- (4-dodecylphenyl) anthracen-9-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2.0 g) synthesized by the method of Synthesis Example 13; 4- (4-Bromophenyl) pyridine (1.28 g), Pd-132 (manufactured by John Massey) (72 mg), potassium acetate (0.71 g), toluene (14 ml), t-butanol (1.4 ml) , Water (0.14 ml) was placed in the flask and stirred at reflux temperature for 9 hours under a nitrogen atmosphere. Water was added, the mixture was extracted with hot toluene, concentrated, and purified by silica gel column chromatography (toluene / ethyl acetate = 1/1 (volume ratio)). This was recrystallized from toluene three times, dried at 200 ° C., purified by sublimation at 1 × 10 ⁻⁴ Pa level and 310 ° C., and 4- (4- (10- (4-dodecylphenyl) anthracene- 9-yl) phenyl) pyridine (872 mg) was obtained. The Tg of this compound was not detected.

The structure of the obtained compound was confirmed by NMR measurement and MS spectrum.
¹ H-NMR (CDCl ₃ ): δ = δ = 0.89 (t, 3H, J = 6.9 Hz), 1.29-1.50 (m, 18H), 1.76-1.82 (m , 2H), 2.79 (t, 2H, J = 7.8 Hz), 7.33-7.43 (m, 8H), 7.62 (d, 2H, J = 8.1 Hz), 7.68. -7.77 (m, 6H), 7.89 (d, 2H, J = 8.1 Hz), 8.74-8.75 (m, 2H).
LC / MS (m / e); 576.6 (M + 1), 577.5, 578.5

[Synthesis Example 22] Synthesis of (Compound 1-691)

2- (10- (4′-dodecyl- [1,1′-biphenyl] -4-yl) anthracen-9-yl) -4,4,5,5-tetra synthesized in the same manner as in Synthesis Example 13 Methyl-1,3,2-dioxaborolane (1.0 g), 4- (4-bromophenyl) pyridine (0.56 g), Pd-132 (manufactured by John Massey) (32 mg), potassium acetate (0.32 g) ), Toluene (6 ml), t-butanol (0.6 ml), and water (0.06 ml) were placed in a flask and stirred at reflux temperature for 9 hours under a nitrogen atmosphere. Water was added, the mixture was extracted with hot toluene, concentrated, and purified by silica gel column chromatography (toluene / ethyl acetate = 1/1 (volume ratio)). This was recrystallized from toluene three times, dried at 200 ° C., and purified by sublimation at 1 × 10 ⁻⁴ Pa level and 310 ° C. to give 4- (4- (10- (4′-dodecyl- [1 , 1′-biphenyl] -4-yl) anthracen-9-yl) phenyl) pyridine (153 mg). The Tg of this compound was not detected.

The structure of the obtained compound was confirmed by NMR measurement and MS spectrum.
¹ H-NMR (CDCl ₃ ): δ = 0.89 (t, 3H, J = 6.9 Hz), 1.28-1.37 (m, 18H), 1.67-1.71 (m, 2H) ), 2.70 (t, 2H, J = 7.7 Hz), 7.33-7.39 (m, 6H), 7.54 (d, 2H, J = 8.0 Hz), 7.63 (d , 2H, J = 8.0 Hz), 7.68-7.70 (m, 4H), 7.73-7.75 (m, 2H), 7.80-7.84 (m, 4H), 7 .90 (d, 2H, J = 8 Hz), 8.75-8.76 (m, 2H).
LC / MS (m / e); 652.7 (M + 1), 653.6, 654.6

<Synthesis of compounds used in comparative examples>
[Synthesis Example 23] (Synthesis of 4,4 ′-((2- (4-butylphenyl) anthracene-9,10-diyl) bis (4,1-phenylene) dipyridine)

2,2 ′-(2- (4-Butylphenyl) anthracene-9,10-diyl) bis (4,4,5,5-tetra) synthesized by replacing the dodecyl group in Synthesis Examples 3 to 5 with a butyl group, respectively. Methyl-1,3,2-dioxaborolane) (3.5 g), 4- (4-bromophenyl) pyridine (3.21 g), tetrakis (triphenylphosphine) palladium (0) (114 mg), tripotassium phosphate ( 3.96 g), 1,2,4-trimethylbenzene (35 ml), t-butanol (3.5 ml) and water (0.7 ml) were placed in a flask and stirred at reflux temperature for 6 hours under a nitrogen atmosphere. After completion of heating, the reaction solution was cooled to room temperature and water was added. The precipitated solid was extracted with hot toluene, concentrated under reduced pressure, methanol was added, and the mixture was filtered. The obtained solid was recrystallized from toluene repeatedly, and this was vacuum-dried, and then purified by sublimation on the order of 10 ⁻³ Pa at 350 ° C. to give 4,4 ′-((2- (4-butylphenyl ) Anthracene-9,10-diyl) bis (4,1-phenylene) dipyridine (734 mg) was obtained, Tg of this compound was not detected.

The structure of the compound obtained by NMR measurement and MS spectrum was confirmed.
¹ H-NMR (CDCl ₃ ): δ = 0.92 (t, 3H, J = 7.4 Hz), 1.32-1.40 (m, 2H), 1.57-1.63 (m, 2H) ), 2.62 (t, 2H, J = 7.8 Hz), 7.21-7.23 (m, 2H), 7.36-7.40 (m, 2H), 7.47-7.48. (M, 2H), 7.64-7.66 (m, 5H), 7.69-7.71 (m, 4H), 7.73-7.76 (m, 2H), 7.81-7 .83 (m, 1H), 7.91-7.93 (m, 5H), 8.75-8.77 (m, 4H).
LC / MS (m / e); 617.7 (M + 1), 618.6, 619.6

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

The organic EL elements according to Examples 1 to 4 and Comparative Examples 1 to 2 were prepared, and after measuring the driving voltage (V) and external quantum efficiency (%) at 1000 cd / m ² emission, respectively, the current density was 37.5 mA. The luminance retention rate when driven at a constant current of / cm ² was measured.

  Note that the quantum efficiency of a light-emitting element includes an internal quantum efficiency and an external quantum efficiency. The ratio of external energy injected as electrons (or holes) into the light-emitting layer of the light-emitting element is converted into photons purely. What is shown is the internal quantum efficiency. On the other hand, the external quantum efficiency is calculated based on the amount of photons emitted to the outside of the light emitting element, and some of the photons generated in the light emitting layer are absorbed inside the light emitting element. The external quantum efficiency is lower than the internal quantum efficiency because it is continuously reflected and is not emitted outside the light emitting element.

The external quantum efficiency is measured as follows. A voltage / current generator R6144 manufactured by Advantest Corporation was used to apply a voltage at which the luminance of the element was 1000 cd / m ² to cause the element to emit light. Using a spectral radiance meter SR-3AR manufactured by TOPCON, the spectral radiance in the visible light region was measured from the direction perpendicular to the light emitting surface. Assuming that the light emitting surface is a completely diffusing surface, the value obtained by dividing the measured spectral radiance value of each wavelength component by the wavelength energy and multiplying by π is the number of photons at each wavelength. Next, the number of photons in the entire wavelength region observed was integrated to obtain the total number of photons emitted from the device. The value obtained by dividing the applied current value by the elementary charge is the number of carriers injected into the device, and the number obtained by dividing the total number of photons emitted from the device by the number of carriers injected into the device is the external quantum efficiency.

Table 1 below shows the material configuration of each layer in the produced organic EL elements according to Examples 1 to 4 and Comparative Examples 1 and 2. For Examples 1 and 2 and Comparative Example 1, organic EL devices in which the electron transport layer was formed of a mixture of the following compound and Liq were also produced.

In Table 1, “HI1” is N ⁴ , N ^{4 ′} -diphenyl-N ⁴ , N ^{4 ′} -bis (9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl] -4, 4′-diamine (Tg = 150.3 ° C.), “HI2” is 1,4,5,8,9,12-hexaazatriphenylene-2,3,6,7,10,11-hexacarbonitrile (this Tg of the compound was not detected), “HT” is N-([1,1′-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazole) -3-yl) phenyl) -9H-fluoren-2-amine (Tg = 127.8 ° C.), “BH1” is 9-phenyl-10- (4-phenylnaphthalen-1-yl) anthracene (Tg = 121. 2 ° C.), “BD1” is 7,7-dimethyl-N ⁵ , N ⁹ -diphenyl-N ⁵ , N ⁹ -bis (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluorene-5,9-diamine (Tg = 120.1 ° C.), compound (A) is 4,4 ′-((2-phenylanthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine (Tg = 144.8 ° C.), compound (B) is 4,4 ′-((2 -(4-Butylphenyl) anthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine (Tg of this compound was not detected). The chemical structure is shown below together with quinolinol lithium (Liq).

<Example 1>
<Element Using Compound (1-1) as Electron Transport Material>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI1, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat containing BH1, molybdenum vapor deposition boat containing BD1, molybdenum vapor deposition boat containing compound (1-1) of the present invention, molybdenum vapor deposition containing Liq A boat, a molybdenum vapor deposition boat containing magnesium, and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI1 is heated to deposit to a film thickness of 40 nm to form a first hole injection layer, and HI2 Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH1 and the vapor deposition boat containing BD1 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH1 to BD1 was approximately 95: 5. The deposition rate of each layer was 0.01 to 1 nm / second. Next, the evaporation boat containing the compound (1-1) was heated and evaporated to a film thickness of 30 nm to form an electron transport layer. The deposition rate for forming the electron transport layer was 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

  By storing the organic EL device obtained above for 20 minutes in a thermostat set to 100 ° C. (room temperature or higher and the temperature range of the lowest glass transition temperature Tg or less of the materials constituting the device), An organic EL element was annealed. Then, the organic EL element was taken out from the thermostatic bath, and naturally cooled until lowered to room temperature.

With respect to the organic EL element before the annealing treatment, when the characteristics at 1000 cd / m ² emission were measured using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the driving voltage was 3.8 V (after the annealing treatment, about 3. 1V), the external quantum efficiency was 4.7%. Moreover, as a result of setting the luminance obtained at a current density of 37.5 mA / cm ² to the initial luminance and conducting the constant current driving test, the time for maintaining the luminance of 80% or more of the initial luminance was 225 hours. .

In addition, the basic production method is the same as in Example 1, and an electron transport layer made of a mixture of both compounds is formed by simultaneously depositing the compound (1-1) and Liq so that the weight ratio is approximately 1: 1. The formed organic EL element was also produced. However, annealing treatment was not performed. When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, the driving voltage was 3.7 V and the external quantum efficiency was 6.1%. Further, the time for maintaining the brightness of 80% or more of the initial brightness was 300 hours.

<Example 2>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) as the electron transport material was changed to the compound (1-61). Annealing treatment was performed in the same manner. For the organic EL element before the annealing treatment, the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1. The driving voltage was 4.1 V (about 3.3 V after the annealing treatment), and the external quantum efficiency was 4.7%. The time for maintaining the brightness of 80% or more of the initial brightness was 83 hours.

In addition, the basic production method is the same as in Example 1, and an electron transport layer made of a mixture of both compounds is formed by simultaneous vapor deposition so that the weight ratio of the compound (1-61) and Liq is about 1: 1. The formed organic EL element was also produced. However, annealing treatment was not performed. When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, the driving voltage was 3.8 V and the external quantum efficiency was 5.6%. Further, the time for maintaining the luminance of 80% or more of the initial luminance was 273 hours.

<Example 3>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) as the electron transporting material was changed to the compound (1-535). Annealing treatment was performed in the same manner. For the organic EL element before annealing, the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, and the driving voltage was 3.7 V (about 3.2 V after annealing), and the external quantum efficiency was It was 5.0%. Further, the time for maintaining the luminance of 80% or more of the initial luminance was 247 hours.

<Example 4>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) as the electron transport material was changed to the compound (1-534). Annealing treatment was performed in the same manner. For the organic EL element before the annealing treatment, the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1. The driving voltage was 3.8 V (about 3.3 V after the annealing treatment), and the external quantum efficiency was It was 5.5%. Further, the time for maintaining the luminance of 80% or more of the initial luminance was 12 hours.

<Comparative Example 1>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) as the electron transporting material was changed to the compound (A). Annealing treatment was performed in the same manner. For the organic EL element before the annealing treatment, when the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, the driving voltage was 3.7 V (about 3.6 V after the annealing treatment), and the external quantum efficiency was It was 4.2%. The time for maintaining the brightness of 80% or more of the initial brightness was 198 hours.

Further, the basic production method was in accordance with Example 1, and an electron transport layer made of a mixture of both compounds was formed by simultaneous vapor deposition so that the weight ratio of the compound (A) and Liq was about 1: 1. An organic EL element was also produced. However, annealing treatment was not performed. When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, the driving voltage was 3.6 V and the external quantum efficiency was 5.3%. The time for maintaining the brightness of 80% or more of the initial brightness was 186 hours.

<Comparative Example 2>
An organic EL device was obtained by the method according to Example 1 except that the compound (1-1) as the electron transport material was changed to the compound (B). Annealing treatment was performed in the same manner. For the organic EL element before the annealing treatment, when the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 1, the driving voltage was 4.3 V (about 4.4 V after the annealing treatment), and the external quantum efficiency was It was 5.0%. Further, the time for maintaining the luminance of 80% or more of the initial luminance was 66 hours.

The organic EL elements according to Examples 5 to 6 and Comparative Example 3 were prepared, and after measuring the driving voltage (V) and external quantum efficiency (%) at 1000 cd / m ² emission, respectively, the current density was 37.5 mA / cm. The luminance retention rate when driving at a constant current of ² was measured.

Table 3 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 5 to 6 and Comparative Example 3.

In Table 3, the compound (C) is 4,4 ′-((2-phenylanthracene-9,10-diyl) bis (3,1-phenylene)) dipyridine (Tg = 1285 ° C.). The chemical structure is shown below.

<Example 5>
<Element Using Compound (1-43) as Electron Transport Material>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI1, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat containing BH1, molybdenum vapor deposition boat containing BD1, molybdenum vapor deposition boat containing compound (1-43) of the present invention, molybdenum vapor deposition containing Liq A boat, a molybdenum vapor deposition boat containing magnesium, and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI1 is heated to deposit to a film thickness of 40 nm to form a first hole injection layer, and HI2 Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH1 and the vapor deposition boat containing BD1 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH1 to BD1 was approximately 95: 5. The deposition rate of each layer was 0.01 to 1 nm / second. Next, the evaporation boat containing the compound (1-43) was heated and evaporated to a thickness of 30 nm to form an electron transport layer. The deposition rate for forming the electron transport layer was 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The driving voltage was 3.3 V and the external quantum efficiency was 4.9%. In addition, as a result of setting the luminance obtained at a current density of 37.5 mA / cm ² to the initial luminance and conducting a constant current driving test, the time for maintaining the luminance of 80% or more of the initial luminance was 12 hours. .

<Example 6>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-43) as the electron transport material was changed to the compound (1-7). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 5, the driving voltage was 4.2 V and the external quantum efficiency was 4.7%. The time for maintaining the brightness of 80% or more of the initial brightness was 82 hours.

<Comparative Example 3>
An organic EL device was obtained by the method according to Example 5 except that the compound (1-43) as the electron transport material was changed to the compound (C). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 5, the driving voltage was 4.4 V and the external quantum efficiency was 4.4%. Further, the time for maintaining the brightness of 80% or more of the initial brightness was 29 hours.

Organic EL elements according to Examples 7 to 8 and Comparative Example 4 were prepared, and after measuring the driving voltage (V) and external quantum efficiency (%) at 1000 cd / m ² emission, respectively, the current density was 37.5 mA / cm. The luminance retention rate when driving at a constant current of ² was measured.

Table 5 below shows the material configuration of each layer in the manufactured organic EL elements according to Examples 7 to 8 and Comparative Example 4.

<Example 7>
<Element Using Compound (1-1) as Electron Transport Material>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI1, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat containing BH1, molybdenum vapor deposition boat containing BD1, molybdenum vapor deposition boat containing compound (1-1) of the present invention, molybdenum vapor deposition containing Liq A boat, a molybdenum vapor deposition boat containing magnesium, and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI1 is heated to deposit to a film thickness of 40 nm to form a first hole injection layer, and HI2 Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH1 and the vapor deposition boat containing BD1 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH1 to BD1 was approximately 95: 5. The deposition rate of each layer was 0.01 to 1 nm / second. Next, the deposition boat containing the compound (1-1) and the deposition boat containing Liq are heated at the same time so that the weight ratio of the deposition boat is about 1: 1, and vapor deposition is performed to a film thickness of 30 nm. A layer was formed. The deposition rate for forming the electron transport layer was 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

When the characteristics at the time of light emission of 1000 cd / m ² were measured using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the driving voltage was 3.7 V and the external quantum efficiency was 6.1%. Further, the luminance obtained when the current density was 37.5 mA / cm ² was set to the initial luminance, and the constant current driving test was performed. As a result, the time for maintaining the luminance of 80% or more of the initial luminance was 300 hours. .

<Example 8>
An organic EL device was obtained by the method according to Example 7 except that the compound (1-1) as the electron transporting material was changed to the compound (1-61). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 7, the driving voltage was 3.8 V and the external quantum efficiency was 5.6%. Further, the time for maintaining the luminance of 80% or more of the initial luminance was 273 hours.

<Comparative Example 4>
An organic EL device was obtained by the method according to Example 7 except that the compound (1-1) as the electron transport material was changed to the compound (A). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 7, the driving voltage was 3.6 V and the external quantum efficiency was 5.3%. The time for maintaining the brightness of 80% or more of the initial brightness was 186 hours.

An organic EL element according to Example 9 and Comparative Example 5 was prepared, and after measuring the driving voltage (V) and external quantum efficiency (%) at the time of light emission of 1000 cd / m ² , the current density was 37.5 mA / cm ² . The luminance retention rate when driving at constant current was measured.

Table 7 below shows the material configuration of each layer in the manufactured organic EL elements according to Example 9 and Comparative Example 5.

In Table 7, compound (D) is 4- (4- (10- [1,1′-biphenyl] -4-yl) anthracen-9-yl) phenyl) pyridine (Tg of this compound was not detected). is there. The chemical structure is shown below.

<Example 9>
<Element Using Compound (1-691) as Electron Transport Material>
A glass substrate of 26 mm × 28 mm × 0.7 mm (manufactured by Optoscience Co., Ltd.) obtained by polishing ITO deposited to a thickness of 180 nm by sputtering to 150 nm was used as a transparent support substrate. This transparent support substrate is fixed to a substrate holder of a commercially available vapor deposition apparatus (made by Showa Vacuum Co., Ltd.), a molybdenum vapor deposition boat containing HI1, a molybdenum vapor deposition boat containing HI2, and a molybdenum vapor containing HT. Vapor deposition boat, molybdenum vapor deposition boat containing BH1, molybdenum vapor deposition boat containing BD1, molybdenum vapor deposition boat containing compound (1-691) of the present invention, molybdenum vapor deposition containing Liq A boat, a molybdenum vapor deposition boat containing magnesium, and a molybdenum vapor deposition boat containing silver were mounted.

The following layers were sequentially formed on the ITO film of the transparent support substrate. The vacuum chamber is depressurized to 5 × 10 ⁻⁴ Pa, and first, a vapor deposition boat containing HI1 is heated to deposit to a film thickness of 40 nm to form a first hole injection layer, and HI2 Is heated to a thickness of 5 nm to form a second hole injection layer, and then the evaporation boat containing HT is heated to a thickness of 25 nm. Thus, a hole transport layer was formed by vapor deposition. Next, the vapor deposition boat containing BH1 and the vapor deposition boat containing BD1 were heated at the same time to form a light emitting layer by vapor deposition to a film thickness of 20 nm. The deposition rate was adjusted so that the weight ratio of BH1 to BD1 was approximately 95: 5. The deposition rate of each layer was 0.01 to 1 nm / second. Next, the evaporation boat containing the compound (1-691) was heated and evaporated to a thickness of 30 nm to form an electron transport layer. The deposition rate for forming the electron transport layer was 1 nm / second.

  Thereafter, the evaporation boat containing Liq was heated to deposit at a deposition rate of 0.01 to 0.1 nm / second so as to have a film thickness of 1 nm. Next, a boat containing magnesium and a boat containing silver were heated at the same time and evaporated to a film thickness of 100 nm to form a cathode. At this time, the vapor deposition rate was adjusted so that the atomic ratio of magnesium and silver was 10: 1, and the organic EL device was obtained so that the vapor deposition rate was 0.01 to 2 nm / second.

Using the ITO electrode as the anode and the Liq / magnesium + silver electrode as the cathode, the characteristics at 1000 cd / m ² emission were measured. The driving voltage was 3.3 V and the external quantum efficiency was 4.4%. Moreover, as a result of setting the luminance obtained at a current density of 37.5 mA / cm ² to the initial luminance and conducting a constant current driving test, the time for maintaining the luminance of 80% or more of the initial luminance was 218 hours. .

<Comparative Example 5>
An organic EL device was obtained by the method according to Example 9 except that the compound (1-691) as the electron transport material was changed to the compound (D). When the characteristics at 1000 cd / m ² emission were measured in the same manner as in Example 9, the driving voltage was 3.5 V and the external quantum efficiency was 4.5%. Further, the time for maintaining the luminance of 80% or more of the initial luminance was 15 hours.

  The organic EL element using the anthracene derivative represented by the general formula (1) of the present invention has a low driving voltage and a long life. For this reason, it is useful as an organic EL element assumed to be used for a long time.

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

Claims (24)

Anthracene derivatives represented by the following general formula (1).

(In general formula (1),
1a, 1b, 2a, 2b, 3a, 3b, 4a and 4b are each independently 0 or 1, at least one is 1,
Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ²² , Ar ³¹ , Ar ³² , Ar ⁴¹ and Ar ⁴² are each independently substituted or unsubstituted phenylene, naphthalenediyl, anthracenediyl, or pyridinediyl; At least one is pyridinediyl;
1c, 2c, 3c and 4c are each independently an integer of 1 to 5,
R ^{1 to} R ⁴ are each independently hydrogen, a substituted or unsubstituted aliphatic group, or a substituted or unsubstituted substantially linear or linear aliphatic group having 8 to 26 carbon atoms. , At least one is a substituted or unsubstituted, substantially linear or linear aliphatic group having 8 to 26 carbon atoms, and any carbon of the substantially linear or linear aliphatic group is- O—, —SiR ₂ — (R is alkyl having 1 to 4 carbon atoms) or cyclohexanediyl may be substituted, but —O—, —SiR ₂ —, cyclohexanediyl, or a combination thereof is successively substituted. And nothing
n and m are each independently an integer of 1 to 4. ) 1c is 1, R ¹ is hydrogen,
2c is 1 or 2, n is 1 or 2,
3c is 1, R ³ is hydrogen,
4a and 4b are 0, 4c is 1, m is 1, R ⁴ is hydrogen,
The substituent when Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ²² , Ar ³¹ and Ar ³² are substituted is alkyl, and
When R ² is substituted, the substituent is alkyl, cycloalkyl, aryl, or halogen;
The anthracene derivative according to claim 1. 1a and 1b are 1, Ar ¹¹ and Ar ³¹ are the same, Ar ¹² and Ar ³² are the same, and
2c is 1 and n is 1.
The anthracene derivative according to claim 2. 2b is 0,
When Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ³¹ and Ar ³² are substituted, the substituent is alkyl having 1 to 4 carbon atoms, and
R ² is a substituted or unsubstituted substantially linear or linear aliphatic group having 8 to 26 carbon atoms, and when substituted, the substituent is alkyl having 1 to 4 carbon atoms, cyclohexyl, phenyl , Naphthyl, anthracenyl, or fluorine,
The anthracene derivative according to claim 3. Ar ¹¹ and Ar ³¹ are phenylene, Ar ¹² and Ar ³² are pyridinediyl,
Ar ²¹ is unsubstituted phenylene, naphthalenediyl, anthracenediyl, or pyridinediyl, and
R ² is unsubstituted straight chain alkyl having 8 to 20 carbon atoms,
The anthracene derivative according to claim 4. Ar ¹¹ , Ar ¹² , Ar ³¹ and Ar ³² are pyridinediyl;
Ar ²¹ is unsubstituted phenylene, naphthalenediyl, anthracenediyl, or pyridinediyl, and
R ² is unsubstituted straight chain alkyl having 8 to 20 carbon atoms,
The anthracene derivative according to claim 4. The anthracene derivative according to claim 5 or 6, wherein 2a is 1 and Ar ²¹ is phenylene.   The anthracene derivative according to claim 5 or 6, wherein 2a is 0. The anthracene derivative according to claim 7 or 8, wherein R ² is straight-chain alkyl having 10 to 14 carbon atoms. 1c is 1 or 2,
2b is 0, 2c is 1, n is 1, R ² is hydrogen,
3c is 1, R ³ is hydrogen,
4a and 4b are 0, 4c is 1, m is 1, R ⁴ is hydrogen,
The substituent when Ar ¹¹ , Ar ¹² , Ar ²¹ , Ar ³¹ and Ar ³² are substituted is alkyl, and
The substituent when R ¹ is substituted is alkyl, cycloalkyl, aryl, or halogen,
The anthracene derivative according to claim 1. 1a is 1, 1c is 1,
2a is 0,
3a and 3b are 1,
When Ar ¹¹ , Ar ¹² , Ar ³¹ and Ar ³² are substituted, the substituent is alkyl having 1 to 4 carbon atoms, and
R ¹ is a substituted or unsubstituted substantially linear or linear aliphatic group having 8 to 26 carbon atoms, and when substituted, the substituent is alkyl having 1 to 4 carbon atoms, cyclohexyl, phenyl , Naphthyl, anthracenyl, or fluorine,
The anthracene derivative according to claim 10. ^12. Ar ¹¹ , Ar ¹² , Ar ³¹ and Ar ³² are each independently unsubstituted phenylene, naphthalenediyl, anthracenediyl, or pyridinediyl, and at least one is pyridinediyl. Anthracene derivatives of Ar ¹¹ , Ar ¹² and Ar ³¹ are phenylene, Ar ³² is pyridinediyl, and
R ¹ is unsubstituted straight chain alkyl having 8 to 20 carbon atoms,
The anthracene derivative according to claim 12. The anthracene derivative according to claim 13, wherein R ¹ is straight-chain alkyl having 10 to 14 carbon atoms. Formula (1-1), Formula (1-7), Formula (1-37), Formula (1-43), Formula (1-61), Formula (1-534), Formula (1-535), The anthracene derivative according to claim 1, which is represented by the formula (1-690) or the formula (1-691).

  A self-assembled material of the anthracene derivative according to any one of claims 1 to 15.   The electron transport material containing the self-organization material of Claim 16.   An organic electroluminescent element which has a pair of electrode which consists of an anode and a cathode, and the organic layer containing the anthracene derivative in any one of Claims 1-15.   (1) forming an organic layer containing the anthracene derivative by vapor deposition at 0.01 to 20.0 nm / second, and / or (2) during or after the production of the organic electroluminescent device, The organic electroluminescent element according to claim 18, comprising an anthracene derivative that is self-organized by performing a heat treatment in a temperature range equal to or lower than the lowest glass transition temperature Tg among the materials constituting the element.   The electron transport containing the electron transport material of Claim 17 arrange | positioned between a pair of electrode which consists of an anode and a cathode, the light emitting layer arrange | positioned between this pair of electrodes, and the said cathode and this light emitting layer An organic electroluminescent device having a layer and / or an electron injection layer.   At least one of the electron transport layer and the electron injection layer further contains at least one selected from the group consisting of quinolinol-based metal complexes, pyridine derivatives, bipyridine derivatives, phenanthroline derivatives, borane derivatives, and benzimidazole derivatives. The organic electroluminescent element according to claim 20.   At least one of the electron transport layer and the electron injection layer may further include an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, alkaline earth Containing at least one selected from the group consisting of metal halides, rare earth metal oxides, rare earth metal halides, alkali metal organic complexes, alkaline earth metal organic complexes and rare earth metal organic complexes, The organic electroluminescent element according to claim 20 or 21.   The display apparatus provided with the organic electroluminescent element in any one of Claims 18-22.   The illuminating device provided with the organic electroluminescent element in any one of Claims 18-22.

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