JP2010135819A - Organic electroluminescent device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent device excellent in luminescence characteristics (luminescence quantum efficiency, drive voltage, durability). <P>SOLUTION: The organic electroluminescent device has at least one organic layer containing a light emitting layer between a pair of electrodes, and the organic electroluminescent device contains at least one kind of compound represented by a formula (I) in at least one organic layer. In the formula (I), X<SP>1</SP>-X<SP>15</SP>represent atoms each of which is selected from carbon or nitrogen, and any one of X<SP>1</SP>-X<SP>8</SP>represents a nitrogen atom. M represents a bivalent metal ion. L<SP>1</SP>represents a bivalent bonding group. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an organic electroluminescent element (hereinafter also referred to as “organic EL element”), and particularly relates to an organic electroluminescent element having excellent light emission characteristics.

  In recent years, organic electroluminescence devices have been actively researched and developed because they can emit light with high luminance when driven at a low voltage. In general, an organic EL element is composed of an organic layer including a light emitting layer and a pair of electrodes sandwiching the layer. Electrons injected from the cathode and holes injected from the anode are recombined in the light emitting layer and generated. The energy of the excitons is used for light emission.

  In recent years, the use of phosphorescent light emitting materials has led to higher efficiency of devices. As phosphorescent materials, iridium complexes and platinum complexes are known (see, for example, Patent Document 1 and Patent Document 2), but no device has been developed that achieves both high efficiency and high durability. At present, the development of phosphorescent materials that can be used is eagerly desired.

A tetradentate ligand consisting of a tetradentate ligand having one azine ring, one azole ring and two aromatic hydrocarbon rings, and the nitrogen atom of the azine ring and the nitrogen atom of the azole ring form a coordinate bond with the platinum atom. An organic electroluminescent element containing a coordination platinum complex (for example, Patent Documents 3 and 4) in a light emitting layer is disclosed. It was not sufficient in terms of light emission quantum efficiency, driving voltage, and durability, and further improvements were demanded.
US Pat. No. 6,303,238 International Publication No. 00/57676 JP 2006-261623 A JP 2008-37848 A

  An object of the present invention is to provide an organic electroluminescence device having excellent light emission characteristics (light emission quantum efficiency, drive voltage, durability).

  As a result of studying the above problems, the present inventors have added the compound represented by the general formula (I) to the organic layer, thereby improving the light emission quantum efficiency of the organic EL device and reducing the driving voltage. And it discovered that it was excellent in the point of durability, and came to this invention. In other words, the above-described problem could be solved by the following means.

[1]
An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, wherein the organic electroluminescent device contains at least one compound represented by the following general formula (I) in at least one organic layer .

In the general formula (I), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , and X ⁸ represents a nitrogen atom. X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently substituted if further replaceable It may have a group. M represents a divalent metal ion. L ¹ represents a divalent linking group. A broken line representing a bond between a metal and a nitrogen atom represents a coordination bond, and a solid line representing a bond between the metal and a carbon atom represents a covalent bond.

[2]
The organic electroluminescent element as described in [1], wherein the general formula (I) is represented by the following general formula (II).

In the general formula (II), X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , and X ²⁸ represents a nitrogen atom. X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently substituted if further replaceable It may have a group. L ² represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

[3]
The organic electroluminescent element according to [2], wherein the general formula (II) is represented by the following general formula (III).

一般式（ＩＩＩ）中、Ｘ⁴¹、Ｘ⁴²、Ｘ⁴³、Ｘ⁴⁴、Ｘ⁴⁵、Ｘ⁴⁶、Ｘ⁴⁷、Ｘ⁴⁸、Ｘ⁵¹、Ｘ⁵²、Ｘ⁵³、Ｘ⁵⁴、及びＸ⁵⁵は、各々独立に炭素又は窒素から選択される原子を表し、Ｘ⁴¹、Ｘ⁴²、Ｘ⁴³、及びＸ⁴⁴のいずれか１つは窒素原子を表す。Ｘ⁴¹、Ｘ⁴²、Ｘ⁴³、Ｘ⁴⁴、Ｘ⁴⁵、Ｘ⁴⁶、Ｘ⁴⁷、Ｘ⁴⁸、Ｘ⁵¹、Ｘ⁵²、Ｘ⁵³、Ｘ⁵⁴、及びＸ⁵⁵が更に置換可能な場合は各々独立に置換基を有していてもよい。Ｌ³は二価の連結基を表す。白金原子と窒素原子の結合を表す破線は配位結合を表し、白金原子と炭素原子の結合を表す実線は共有結合を表す。

In the general formula (III), X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ⁴¹ , X ⁴² , X ⁴³ , and X ⁴⁴ represents a nitrogen atom. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently substituted if further replaceable It may have a group. L ³ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

[4]
The organic electroluminescent device as described in [3], wherein the general formula (III) is represented by the following general formula (IV).

In the general formula ^{(IV), X 61, X} 62, X 63, X 64, X 65, X 66, X 67, and X ⁶⁸ represents an atom selected from carbon or nitrogen independently, X ^61, Any one of X ⁶² , X ⁶³ and X ⁶⁴ represents a nitrogen atom. When X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , and X ⁶⁸ can be further substituted, each may independently have a substituent. R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , and R ⁶⁵ each independently represent a hydrogen atom or a substituent. L ⁴ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

[5]
The organic electroluminescent element as described in [4], wherein the general formula (IV) is represented by the following general formula (V).

In the general formula (V), X ⁷¹ , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , X ⁷⁷ , and X ⁷⁸ each independently represent an atom selected from carbon or nitrogen. When X ⁷¹ , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , X ⁷⁷ , and X ⁷⁸ can be further substituted, each may independently have a substituent. R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , and R ⁷⁵ each independently represent a hydrogen atom or a substituent. L ⁵ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

[6]
Furthermore, the organic electroluminescent element according to any one of [1] to [5], wherein a material having at least one deuterium atom is contained in any one of the organic layers.
[7]
Furthermore, the light emitting layer contains the material which has at least 1 deuterium atom, The organic electroluminescent element in any one of [1]-[5] characterized by the above-mentioned.
[8]
The organic electroluminescence according to any one of [6] and [7], wherein the material having at least one deuterium atom is a material having a carbazole skeleton or an indole skeleton having at least one deuterium atom element.
[9]
Furthermore, the organic electroluminescent element in any one of [1]-[8] characterized by including the compound represented by the following general formula (a) in a light emitting layer.

In the general formula (a), R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an acyl group, an acyloxy group, an amino group, a nitro group, Represents a group, a cyano group, an ester group, an amide group, a halogen group, a perfluoroalkyl group, or a silyl group, and at least one of R _{1 to} R ₄ is a group having a double bond or a triple bond. X _{1 to} X ₁₂ are each independently a hydrogen atom, alkyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, acyl group, acyloxy group, amino group, nitro group, cyano group, ester group, amide group Represents a halogen group, a perfluoroalkyl group, or a silyl group.

  The organic electroluminescent device of the present invention has a high external quantum efficiency and is excellent in driving voltage and durability.

  In the present specification, the compounds represented by the general formulas (I), (II), (III), (IV), and (V) (synonymous with the general formulas (I) to (V)) are “ It is used synonymously with “the compound of the present invention” and “the complex of the present invention”. Moreover, the organic electroluminescent element which has an organic layer containing the compound of this invention is used synonymously with the element of this invention. In this specification, the substituent group A is defined as follows.

(Substituent group A)
An alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n- Decyl, n-hexadecyl, trifluoromethyl, pentafluoroethyl, etc.), a cycloalkyl group (preferably having 3 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 3 to 10 carbon atoms). For example, cyclopropyl, cyclopentyl, cyclohexyl, etc.), an alkenyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms such as vinyl, And allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl groups (preferably having 2 to 3 carbon atoms) , More preferably from 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl and 3-pentynyl.)

An aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, naphthyl, anthranyl and the like), amino. Group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, such as amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, etc. An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc. An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably carbon 6 to 20, particularly preferably 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, and the like, and heterocyclic oxy groups (preferably having 1 to 30 carbon atoms, more preferably Is a C1-C20, particularly preferably C1-C12, for example, pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy and the like.

An acyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group ( Preferably it has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonyl, ethoxycarbonyl and the like, and an aryloxycarbonyl group (preferably having a carbon number). 7 to 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonyl, and acyloxy groups (preferably 2 to 30 carbon atoms, more preferably carbon atoms). 2 to 20, particularly preferably 2 to 10 carbon atoms, for example, acetoxy, benzoyloxy And the like.), An acylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetylamino or benzoylamino.)

An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino), aryloxycarbonylamino group ( Preferably it has 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonylamino, etc., and a sulfonylamino group (preferably 1 to 1 carbon atoms). 30, More preferably, it is C1-C20, Most preferably, it is C1-C12, for example, methanesulfonylamino, benzenesulfonylamino, etc.), a sulfamoyl group (preferably C0-30, more preferably) Has 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms. Amoiru, methylsulfamoyl, dimethylsulfamoyl, and the like phenylsulfamoyl.)

A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like), alkylthio. A group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methylthio and ethylthio), an arylthio group (preferably having 6 to 6 carbon atoms). 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio, and the like, and a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 carbon atom). -20, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2-benzimidazolyl Oh, 2-benzoxazolyl thio, and 2-benzthiazolylthio and the like.)

A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl), a sulfinyl group (preferably having 1 carbon atom). To 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), ureido groups (preferably 1 to 30 carbon atoms, more preferably C1-C20, Most preferably, it is C1-C12, for example, a ureido, methylureido, phenylureido etc. are mentioned), phosphoric acid amide groups (preferably C1-C30, more preferably carbon number) 1 to 20, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphoric acid amide and phenyl phosphoric acid amide That.), Hydroxy group, a mercapto group, a halogen atom (e.g. fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or more preferably fluorine atom)

Cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, As, for example, nitrogen atom, oxygen atom, sulfur atom, specifically imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc. ), A silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl), silyloxy group (Preferably 3 to 40 carbon atoms, more preferably 3 to 3 carbon atoms. , Particularly preferably 3 to 24 carbon atoms, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like. These substituents may be further substituted.

  The hydrogen atoms in the explanation of the general formulas (I) to (V) include isotopes (deuterium atoms and the like), and further, the atoms constituting the substituents also include the isotopes.

  In the description of the general formulas (I) to (V), the coordination bond represents a bond formed between a neutral ligand and a metal, and the covalent bond is between an anionic ligand and a metal cation. Means a bond formed by

[Organic electroluminescence device]
The organic electroluminescent element of the present invention is an organic electroluminescent element having at least one organic layer including a light emitting layer between a pair of electrodes, and at least one compound represented by the following general formula (I): Contained in the organic layer.

  The general formula (I) will be described.

In the general formula (I), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , and X ⁸ represents a nitrogen atom. X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently substituted if further replaceable It may have a group. M represents a divalent metal ion. L ¹ represents a divalent linking group. A broken line representing a bond between a metal and a nitrogen atom represents a coordination bond, and a solid line representing a bond between the metal and a carbon atom represents a covalent bond.

When X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ can be further substituted, the following substituent group You may have each independently the substituent selected from the substituent containing A. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups. Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring Group, silyl group, more preferably a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, amino group, alkoxy group, aryloxy group, cyano group, fluorine atom, heterocyclic ring, and more preferably, Methyl group, trifluoromethyl , A fluorine atom, a methoxy group, an aryl group, a cyano group.

  M represents a divalent metal ion. The preferred metal species are platinum atom, palladium, nickel, zinc and copper, more preferably platinum, palladium and nickel, and most preferably platinum.

In the general formula (I), L ¹ represents a divalent linking group. The linking group is not particularly limited, but a divalent linking group consisting of a single bond, a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom, a silicon atom, or a germanium atom is particularly preferable, and is selected from the following linking group group A. The group is particularly preferred.

Linking group A

In the connecting group A, R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , R ⁸⁶ , R ⁸⁷ , R ⁸⁸ , R ⁸⁹ , R ⁹⁰ , R ⁹¹ , and R ⁹² (R ^{81 to} R ⁹² ) are Each independently represents a hydrogen atom or a substituent selected from substituents including substituent group A. When R ^{81 to} R ⁹² represent a substituent, the substituent is preferably a substituent selected from the substituent group A. When R ^{81 to} R ⁹² can be substituted, they may further have a substituent, and R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , R ⁸⁵ and R ⁸⁶ , R ⁸³ and R ⁸⁵ , R ⁸³ and R ⁸⁶ , R ⁸⁴ and R ⁸⁶ , or R ⁹⁰ and R ⁹¹ may be bonded to each other to form a ring.

L ¹ is preferably a substituent selected from the linking group A, and of these, —C (R ⁸¹ ) (R ⁸² ) —, —C (R ⁸³⁾ (R ⁸⁴ ) C (R ⁸⁵ ) (R ⁸⁶ )-, -Si (R ⁸⁷ ) (R ⁸⁸ )-, -N (R ⁸⁹ )-, -O-, -S-, -SO-, -SO _2- , or -CO- are preferred, and -C ( ^R81 ) ( ^R82 )-, -C ( ^R83 ) ( ^R84 ) C ( ^R85 ) ( ^R86 )-, -Si ( ^R87 ) ( ^R88 )-, -O-, or -S- Are more preferable, and —C (R ⁸¹ ) (R ⁸² ) —, —C (R ⁸³ ) (R ⁸⁴ ) C (R ⁸⁵ ) (R ⁸⁶ ) — are more preferable.

In the —C (R ⁸¹ ) (R ⁸² ) —, R ⁸¹ and R ⁸² are preferably a hydrogen atom or a substituent selected from the following substituent group B.

(Substituent group B)
Substituents are alkyl groups, cycloalkyl groups, aryl groups, halogen atoms, amino groups, alkylthio groups, arylthio groups, alkyloxy groups, aryloxy groups, hydroxy groups, mercapto groups, and halogen atoms, more preferably alkyl groups. , A cycloalkyl group, an aryl group, a halogen atom, an alkylthio group, an arylthio group, an alkyloxy group, an aryloxy group and a halogen atom, more preferably an alkyl group and an aryl group.

In the —C (R ⁸³ ) (R ⁸⁴ ) C (R ⁸⁵ ) (R ⁸⁶ ) —, R ⁸³ , R ⁸⁴ , R ⁸⁵ and R ⁸⁶ are preferably a hydrogen atom or a substituent selected from the substituent group B. is there.

In the —Si (R ⁸⁷ ) (R ⁸⁸ ) —, R ⁸⁷ and R ⁸⁸ are preferably a hydrogen atom or a substituent selected from the substituent group B.

In the —Ge (R ⁹⁰ ) (R ⁹¹ ) —, R ⁹⁰ and R ⁹¹ are preferably a hydrogen atom or a substituent selected from the substituent group B.

In the —N (R ⁸⁹ ) —, R ⁸⁹ is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or an aryl group, and still more preferably an aryl group.

In the above -P (R ⁹² ) —, R ⁹² has the same ^{meaning as} the preferred range of R ⁸⁹ .

  In the present invention, the compound represented by the general formula (I) is preferably a compound represented by the general formula (II).

  The general formula (II) will be described.

In the general formula (II), X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , and X ²⁸ represents a nitrogen atom. X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently substituted if further replaceable It may have a group. L ² represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

In the general formula (II), X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , X ³⁵ , and L ² are X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , X ¹⁵ , and L ¹ in general formula (I) It is synonymous and the preferred range is also synonymous.

In the present invention, the compound represented by the general formula (II) is preferably a compound represented by the general formula (III).
The general formula (III) will be described.

In the general formula (III), X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ⁴¹ , X ⁴² , X ⁴³ , and X ⁴⁴ represents a nitrogen atom. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently substituted if further replaceable It may have a group. L ³ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

In the general formula (III), X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , X ⁵⁵ , and L ³ are X ³¹ , X ³² , X ³³ , X ³⁴ , X ³⁵ , and L ^{2 in the} general formula (II). The preferred range is also synonymous. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , and X ⁴⁸ each independently represent an atom selected from carbon or nitrogen, and X ⁴¹ , X ⁴² , X ⁴³ , and Any one of X ⁴⁴ represents a nitrogen atom.

When X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , and X ⁴⁸ can be further substituted, each independently has a substituent selected from the substituents including substituent group A. You may do it. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups. Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring Group, silyl group, more preferably a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, amino group, alkoxy group, aryloxy group, cyano group, fluorine atom, heterocyclic ring, and more preferably, Methyl group, trifluoromethyl , A fluorine atom, a methoxy group, an aryl group, a cyano group.

In the present invention, the compound represented by the general formula (III) is preferably a compound represented by the general formula (IV).
The general formula (IV) will be described.

In the general formula ^{(IV), X 61, X} 62, X 63, X 64, X 65, X 66, X 67, and X ⁶⁸ represents an atom selected from carbon or nitrogen independently, X ^61, Any one of X ⁶² , X ⁶³ and X ⁶⁴ represents a nitrogen atom. When X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , and X ⁶⁸ can be further substituted, each may independently have a substituent. R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , and R ⁶⁵ each independently represent a hydrogen atom or a substituent. L ⁴ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

In the general formula (IV), X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , X ⁶⁸ , and L ⁴ are X ⁴¹ , X ⁴² , X ^{43 in the} general formula (III). , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , and L ³ , and the preferred range is also the same. R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , and R ⁶⁵ may each independently have a hydrogen atom or a substituent selected from substituents including substituent group A. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups. Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring Group, silyl group, more preferably a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, amino group, alkoxy group, aryloxy group, cyano group, fluorine atom, heterocyclic ring, and more preferably, Methyl group, trifluoromethyl , A fluorine atom, a methoxy group, an aryl group, a cyano group.

In the present invention, the compound represented by the general formula (IV) is preferably a compound represented by the general formula (V).
The general formula (V) will be described.

In the general formula (V), X ⁷¹ , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , X ⁷⁷ , and X ⁷⁸ each independently represent an atom selected from carbon or nitrogen. When X ⁷¹ , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , X ⁷⁷ , and X ⁷⁸ can be further substituted, each may independently have a substituent. R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , and R ⁷⁵ each independently represent a hydrogen atom or a substituent. L ⁵ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

In the general formula (V), R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , and L ⁵ represent R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , and L in the general formula (IV). ^It is synonymous with ⁴ , and a preferable range is also synonymous. X ⁷¹ , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , X ⁷⁷ , and X ⁷⁸ each independently represent an atom selected from carbon or nitrogen, and X ⁷¹ , X ⁷³ , and X ⁷⁴ are preferably carbon Is an atom. When X ⁷¹ , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , X ⁷⁷ , and X ⁷⁸ are further substitutable, each independently selected from a hydrogen atom or a substituent selected from substituents including substituent group A You may have. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups. Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring Group, silyl group, more preferably a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, amino group, alkoxy group, aryloxy group, cyano group, fluorine atom, heterocyclic ring, and more preferably, Methyl group, trifluoromethyl , A fluorine atom, a methoxy group, an aryl group, a cyano group.

  As a compound represented by general formula (V), one of the preferable forms is a compound represented by the following general formula (VI). General formula (VI) is demonstrated.

In the general formula (VI), X ⁸¹ , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , and X ⁸⁸ each independently represent an atom selected from carbon or nitrogen. When X ⁸¹ , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , and X ⁸⁸ can be further substituted, they may each independently have a substituent. R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , and R ⁸⁵ each independently represent a hydrogen atom or a substituent. n represents an integer of 1 to 4. A cyano group is linked to a C atom in X ⁸⁵ to X ^88. L ⁶ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

In the general formula (VI), R ⁸¹ , R ⁸² , R ⁸³ , R ⁸⁴ , R ⁸⁵ , and L ⁶ are R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , and L in the general formula (V). ^It is synonymous with ⁵ , and a preferable range is also synonymous. X ⁸¹ , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , and X ⁸⁸ each independently represent an atom selected from carbon or nitrogen. X ⁸¹ , X ⁸³ and X ⁸⁴ are preferably carbon atoms. When X ⁸¹ , X ⁸³ , X ⁸⁴ , X ⁸⁵ , X ⁸⁶ , X ⁸⁷ , and X ⁸⁸ are further substitutable, each independently selected from a hydrogen atom or a substituent selected from substituents including substituent group A You may have. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups. Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring Group, silyl group, more preferably a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, amino group, alkoxy group, aryloxy group, cyano group, fluorine atom, heterocyclic ring, and more preferably, Methyl group, trifluoromethyl , A fluorine atom, a methoxy group, an aryl group, a cyano group.

  n represents an integer of 1 to 4, preferably 1 or 2.

In general formula (VI), by substituting at least one carbon atom in X ^{85 to} X ⁸⁸ with a cyano group, electron injection into the organic layer containing general formula (VI) is facilitated, and external An organic electroluminescence device having excellent quantum efficiency can be obtained. In addition, the lifetime of the organic electroluminescent element can be extended.

  As a compound represented by general formula (V), one of the preferable forms is a compound represented by the following general formula (VII). General formula (VII) is demonstrated.

In the general formula (VII), X ⁹¹ , X ⁹³ , X ⁹⁴ , X ⁹⁵ , X ⁹⁶ , X ⁹⁷ , and X ⁹⁸ each independently represent an atom selected from carbon or nitrogen. When X ⁹¹ , X ⁹³ , X ⁹⁴ , X ⁹⁵ , X ⁹⁶ , X ⁹⁷ , and X ⁹⁸ can be further substituted, they may each independently have a substituent. R ⁹¹ , R ⁹³ , R ⁹⁴ , and R ⁹⁵ each independently represent a hydrogen atom or a substituent. B represents a substituent selected from an alkyl group, a cycloalkyl group, an amino group, an alkoxy group, an aryloxy group, and a fluorine atom. L ⁷ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.

In the general formula (VII), R ⁹¹ , R ⁹³ , R ⁹⁴ , R ⁹⁵ , and L ⁷ are synonymous with R ⁷¹ , R ⁷³ , R ⁷⁴ , R ⁷⁵ , and L ^{5 in} the general formula (V), The preferred range is also synonymous. X ⁹¹ , X ⁹³ , X ⁹⁴ , X ⁹⁵ , X ⁹⁶ , X ⁹⁷ , and X ⁹⁸ each independently represent an atom selected from carbon or nitrogen. X ⁹¹ , X ⁹³ and X ⁹⁴ are preferably carbon atoms. When X ⁹¹ , X ⁹³ , X ⁹⁴ , X ⁹⁵ , X ⁹⁶ , X ⁹⁷ , and X ⁹⁸ are further substitutable, each independently selected from a hydrogen atom or a substituent selected from substituents including substituent group A You may have. Preferred substituents include alkyl groups, cycloalkyl groups, aryl groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, acyloxy groups, sulfonylamino groups, sulfamoyl groups, carbamoyl groups. Group, alkylthio group, arylthio group, heterocyclic thio group, sulfonyl group, sulfinyl group, ureido group, phosphoramido group, hydroxy group, mercapto group, halogen atom, sulfo group, carboxyl group, nitro group, sulfino group, heterocyclic ring Group, silyl group, more preferably a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, amino group, alkoxy group, aryloxy group, cyano group, fluorine atom, heterocyclic ring, and more preferably, Methyl group, trifluoromethyl , A fluorine atom, a methoxy group, an aryl group, a cyano group.

  B represents a substituent selected from an alkyl group, a cycloalkyl group, an amino group, an alkoxy group, an aryloxy group, and a fluorine atom. Preferred substituents are an alkyl group, a cycloalkyl group, an amino group, and a fluorine atom, more preferably an alkyl group, a cycloalkyl group, and a fluorine atom, and still more preferably an alkyl group.

  In the general formula (VII), when the substituent of B is the above substituent, the lowest excited triplet energy level of the general formula (VII) is increased, and the emission wavelength can be shortened.

The compounds represented by general formula (I) to general formula (VII) may be polymer compounds having these compounds in the main chain or side chain.
In the case of a high molecular compound, it may be a homopolymer compound or a copolymer, and the copolymer may be a random copolymer, an alternating copolymer, or a block copolymer. In the case of a copolymer, the other monomer is preferably a monomer having a charge transport function portion. Examples of the monomer having a charge transport function include a host material described later, a material contained in a hole transport layer, and a monomer having a partial structure of the compound mentioned as a material contained in an electron transport layer, preferably as a host material. A monomer having the above-mentioned compound in a partial structure.
In the case of a polymer compound, the preferred molecular weight is 2,000 or more and less than 1,000,000, more preferably 10,000 or more and less than 500,000, and still more preferably 10,000 or more and less than 100,000.

  Specific examples of the compound represented by formula (I) in the present invention are illustrated below, but the present invention is not limited thereto.

When the compound of the present invention is represented by the general formula (VIII), partial structures that can be used for Q ^A , Q ^B , Q ^C , Q ^D , and L are shown below. M and L in the partial structures Q ^A , Q ^B , Q ^C , and Q ^D correspond to M and L in the general formula (VIII), respectively, and Q is Q ^B when each partial structure is Q ^A , Q ^B represents Q ^A , Q ^C represents Q ^D , and Q ^D represents Q ^C.

A partial structure which can be used to Q ^A is a partial structure group represented by [QB61CC].
A partial structure which can be used in Q ^B is a partial structure group represented by [QT60CN].
A partial structure which can be used to Q ^C is a partial structure group represented by [QT50NN].
A partial structure which can be used to Q ^D is a partial structure group represented by [QB61CC].
The partial structure that can be used for L is a partial structure group represented by [L].
Two Q partial structure of the [L] is the left side of Q is Q ^B, right Q represents Q ^C.

For example, compounds of general formula shown below as a compound represented by formula (I) is Q ^A in the general formula (VI) represents a QB61CC-151, Q ^B represents QT60CN-1, Q ^C is QT50NN-4 the stands, Q ^D represents QB61CC-1, L represents L-1, M is meant to represent the platinum atom.

  A group of partial structures [QT60CN] is shown below.

  A group of partial structures [QT50NN] is shown below.

  The group [L] of partial structures is shown below.

Specific examples of the compound are illustrated below, but the present invention is not limited to these.

  The compound represented by the general formula (1) or (2) of the present invention can be synthesized by various known synthesis methods. For example, it can be synthesized by using the methods described in Japanese Patent Application No. 2007-96255 and Japanese Patent Application No. 2007-19462.

  Purification of the synthesized compounds can be performed by known methods (for example, “Separation and Purification Technology Handbook (1993, edited by the Chemical Society of Japan),“ High-level separation of trace components and difficult-to-purify substances by chemical conversion methods ”(1988, IPC),“ Experimental chemistry course (4th edition) 1 "(1990, edited by the Chemical Society of Japan)" can be used. Specifically, extraction, adsorption, occlusion, recrystallization, reprecipitation, distillation, sublimation, ion exchange , Filtration, zone melt method, electrophoresis, centrifugation, sedimentation, washing, various chromatography and the like.

  The device of the present invention will be described in more detail.

  The element of the present invention has at least one organic layer including a light emitting layer between a pair of electrodes. When the organic layer is a single layer, the organic layer has a light emitting layer. In view of the properties of the element, at least one of the anode and the cathode is preferably transparent or translucent.

  The element of the present invention is characterized in that the organic layer contains a complex having a tetradentate ligand having a specific structure. Although it does not specifically limit as an organic layer, In addition to a light emitting layer, a positive hole injection layer, a positive hole transport layer, an electron injection layer, an electron transport layer, a positive hole block layer, an electron block layer, an exciton block layer, a protective layer, etc. You may have. Each of these layers may have other functions.

  As an aspect of lamination of the organic layer in the present invention, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are laminated in this order from the anode side is preferable. Further, a charge blocking layer or the like may be provided between the hole transport layer and the light-emitting layer, or between the light-emitting layer and the electron transport layer. A hole injection layer may be provided between the anode and the hole transport layer, and an electron injection layer may be provided between the cathode and the electron transport layer. Each layer may be divided into a plurality of secondary layers.

  Each element constituting the element of the present invention will be described in detail.

<Organic layer>
The organic layer in the present invention will be described. The element of the present invention has at least one organic layer including a light emitting layer, and the organic layer other than the organic light emitting layer includes a hole transport layer, an electron transport layer, and a hole block layer as described above. , Electron blocking layer, hole injection layer, electron injection layer and the like.

-Formation of organic layer-
In the organic electroluminescent element of the present invention, each layer constituting the organic layer can be suitably formed by any of a dry film forming method such as a vapor deposition method and a sputtering method, a transfer method, and a printing method.

-Light emitting layer-
The light-emitting layer receives holes from the anode, the hole injection layer, or the hole transport layer when an electric field is applied, receives electrons from the cathode, the electron injection layer, or the electron transport layer, and recombines holes and electrons. It is a layer which has the function to provide and to emit light.

  The light emitting layer in the present invention may be composed only of a light emitting material, or may be a mixed layer of a host material and a light emitting material. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and the light emitting material may be one kind or two or more kinds. The host material is preferably a charge transport material. The host material may be one kind or two or more kinds, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Furthermore, the light emitting layer may contain a material that does not have charge transporting properties and does not emit light. The light emitting layer is preferably a light emitting material and a host material using the complex of the present invention.

  In addition, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.

  Examples of fluorescent materials that can be used in the present invention include, for example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives. , Condensed aromatic compounds, perinone derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyralidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styryl Complexes of amine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives and pyromethene derivatives Various complexes represented, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

  Examples of phosphorescent materials that can be used in the present invention include, in addition to the compounds of the present invention, for example, US Pat. No. 6,303,238, US Pat. No. 6,097,147, WO 00/57676, WO 00/70655. Pamphlet, WO 01/08230 pamphlet, WO 01/39234 pamphlet, WO 01/41512 pamphlet, WO 02/02714 pamphlet, WO 02/15645 pamphlet, international publication No. 02/44189 pamphlet, International Publication No. 05/19373 pamphlet, JP-A No. 2001-247859, JP-A No. 2002-302671, JP-A No. 2002-117978, JP-A No. 2003-133074, JP 2002-235 No. 76, JP-A No. 2003-123982, JP-A No. 2002-170684, European Patent Application No. 12111257, JP-A No. 2002-226495, JP-A No. 2002-234894, JP-A No. 2001-2001 No. 247859, JP-A No. 2001-298470, JP-A No. 2002-173684, JP-A No. 2002-203678, JP-A No. 2002-203679, JP-A No. 2004-357799, JP-A No. 2006-256999 And phosphorescent compounds described in patent documents such as JP-A No. 2007-19462, JP-A No. 2007-84635, and JP-A No. 2007-96259. Among them, more preferable examples of the light-emitting material include Ir. Complex, Pt complex, Cu complex, Re complex, W complex, Rh complex , Ru complexes, Pd complexes, Os complexes, Eu complexes, Tb complexes, Gd complexes, Dy complexes, and Ce complexes. Particularly preferred is an Ir complex, a Pt complex, or a Re complex, among which an Ir complex or a Pt complex containing at least one coordination mode of a metal-carbon bond, a metal-nitrogen bond, a metal-oxygen bond, and a metal-sulfur bond. Or Re complexes are preferred. Furthermore, from the viewpoints of luminous efficiency, driving durability, chromaticity, etc., an Ir complex, a Pt complex, or a Re complex containing a tridentate or higher polydentate ligand is particularly preferable.

  The compound represented by the general formula (I) of the present invention can be contained in any layer when there are a plurality of organic layers. The complex of the present invention is preferably contained in the light emitting layer, more preferably contained in the light emitting layer as the light emitting material or host material, further preferably contained in the light emitting layer as the light emitting material, and at least one kind It is particularly preferable that it is contained in the light emitting layer together with the host material.

The content of the phosphorescent material (the complex of the present invention and / or the phosphorescent material used together) that can be used in the present invention is in the range of 0.1% by mass to 60% by mass with respect to the total mass of the light emitting layer. The range of 0.2% by mass to 50% by mass is more preferable, the range of 0.3% by mass to 40% by mass is more preferable, and the range of 0.5% by mass to 30% by mass is the most preferable. .
When another phosphorescent material is used in combination with the compound represented by the general formula (I) of the present invention, the content of the compound represented by the general formula (I) of the present invention is the mass of the entire phosphorescent light emitting material. The range of 0.1% by mass to 60% by mass is preferable, the range of 0.2% by mass to 50% by mass is more preferable, and the range of 0.3% by mass to 40% by mass is more preferable. The range of 0.5 mass% or more and 35 mass% or less is most preferable.

  When the compound represented by the general formula (I) of the present invention is introduced into a layer other than the light emitting layer (for example, a charge transport layer), the layer preferably contains 10% by mass to 100% by mass, More preferably, it is contained in 30% by mass to 100% by mass.

  The organic electroluminescent element of the present invention preferably further contains a material having at least one deuterium atom in any of the organic layers. The durability of the compounds represented by the general formulas (I) to (V) of the present invention is further improved by using them together with a material having at least one deuterium atom.

  The material having at least one deuterium atom may be an organic material, an inorganic material, or both, but is preferably an organic material.

The organic material having at least one deuterium atom has a ratio of deuterium atoms to hydrogen atoms (the number of deuterium atoms: the number of hydrogen atoms) at a position where hydrogen atoms or deuterium atoms can be bonded. It means that it is included in the range of 100: 0 to 1:99. Here, the position at which a hydrogen atom or deuterium atom can be bonded may be in any range from at least one specific position to the whole in one molecule. In other words, the said ratio is synonymous with the ratio (deuteration rate) which a deuterium atom occupies in the sum total of the position where a hydrogen atom or a deuterium atom can couple | bond together.
Therefore, the state of the above ratio can be realized by simultaneously using a compound containing deuterium at the position and a compound not containing deuterium at an appropriate ratio.

  The composition range of deuterium atoms and hydrogen atoms is preferably 100: 0 to 5:95, more preferably 100: 0 to 50:50, and particularly preferably 100: 0 to 80:20.

  The material having at least one deuterium atom may be contained in any layer of the organic electroluminescent device, but the hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer, exciton block It is preferably contained in one or more of the charge blocking layer and the charge blocking layer, more preferably contained in one or more of the light emitting layer, exciton blocking layer and charge blocking layer, and contained in the light emitting layer. More preferably, it is preferably contained as a host material in the light emitting layer.

  Examples of the material having at least one deuterium atom include, but are not limited to, compounds described in International Publication No. 02/47440 pamphlet.

  As a material having at least one deuterium atom, an example of a particularly preferable material is preferably a material containing a nitrogen atom, more preferably a material containing a tertiary amine skeleton, a carbazole skeleton, or an indole skeleton, Alternatively, a material including an indole skeleton is more preferable, and a material including a carbazole skeleton is particularly preferable.

  Examples of the material containing a carbazole skeleton having at least one deuterium atom or an indole skeleton include the following.

  Moreover, as a host material contained in the light emitting layer in this invention, the thing which does not have a deuterium atom besides the above can also be used. For example, those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, those having a pyrazine skeleton, those having a triazine skeleton, those having an arylsilane skeleton, Examples thereof include materials exemplified in the sections of the transport layer, the electron injection layer, and the electron transport layer.

  The host material is a compound mainly responsible for charge injection and transport in the light emitting layer, and itself is a compound that does not substantially emit light. In this specification, “substantially no light emission” means that the light emission amount from the substantially non-light emitting compound is preferably 5% or less, more preferably 3% or less of the total light emission amount of the entire device. More preferably, it means 1% or less.

  The concentration of the host material in the light emitting layer is not particularly limited, but is preferably the main component (the component having the largest content) in the light emitting layer, more preferably 50% by mass or more and 99.9% by mass or less, 70 mass% or more and 99.8 mass% or less are still more preferable, 80 mass% or more and 99.7 mass% or less are especially preferable, and 90 mass% or more and 99.5 mass% or less are the most preferable.

  The glass transition point of the host material is preferably 100 ° C. or higher and 500 ° C. or lower, more preferably 110 ° C. or higher and 300 ° C. or lower, and still more preferably 120 ° C. or higher and 250 ° C. or lower.

  The fluorescence wavelength in the film state of the host material contained in the light emitting layer of the present invention is preferably in the range of 400 nm to 650 nm, more preferably in the range of 420 nm to 600 nm, and in the range of 440 nm to 550 nm. More preferably.

  As the host material used in the present invention, the compounds described in paragraphs 0113 to 0161 of JP-A No. 2002-1000047 and the compounds described in paragraphs 0087 to 0098 of JP-A No. 2004-214179 can be suitably used. However, it is not limited to these.

  Although the thickness of a light emitting layer is not specifically limited, Usually, it is preferable that they are 1 nm-500 nm, it is more preferable that they are 5 nm-200 nm, and it is still more preferable that they are 10 nm-100 nm.

The organic electroluminescent element preferably further contains a compound represented by the following general formula (a) in the light emitting layer.
Generally, in charge (electron / hole) injection at the organic thin film interface of stacked organic electronic devices, the difference between the ionization potentials (Ip) and electron affinities (Ea) of two adjacent materials It is known that the smaller the value, the smaller the electric charge injection barrier and the lower the driving voltage of the organic electroluminescent device. In addition to the material Ip and Ea, energy derived from the interaction between the molecules of the material, etc. Levels play an important role. In addition, regarding the movement of charges in the organic layer, by appropriately controlling the interaction between the material molecules, the charge mobility can be increased and the driving voltage of the element can be lowered. By appropriately using the compound represented by the general formula (a) together with the light emitting material, the interaction between the material molecules may be controlled, and as a result, the driving voltage can be reduced.
In addition, a change in an interaction state (for example, an association state) between material molecules when the element is driven may cause a change in element characteristics, resulting in a decrease in element luminance (ie, element lifetime). By using the compound represented by the general formula (a), a stable interaction state is formed in advance, and this problem can be avoided. The compound represented by the general formula (a) used in the organic electroluminescence device of the present invention is excellent in chemical stability, has little alteration such as decomposition of the material during driving of the device, and depends on a decomposition product of the material. In addition, it is possible to prevent a decrease in the efficiency of the organic electroluminescent element and a decrease in the element life.
Next, the compound represented by the general formula (a) used in the organic electroluminescence device of the present invention will be described in detail.

In the general formula (a), R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an acyl group, an acyloxy group, an amino group, a nitro group, Represents a group, a cyano group, an ester group, an amide group, a halogen group, a perfluoroalkyl group, or a silyl group, and at least one of R _{1 to} R ₄ is a group having a double bond or a triple bond. X _{1 to} X ₁₂ are each independently a hydrogen atom, alkyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, acyl group, acyloxy group, amino group, nitro group, cyano group, ester group, amide group Represents a halogen group, a perfluoroalkyl group, or a silyl group.

Examples of the alkyl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (ie, 2-butyl), isobutyl, Examples include tert-butyl, n-pentyl, isopentyl, n-hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.

Examples of the alkenyl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include vinyl, allyl (ie, 1- (2-propenyl)), 1- (1-propenyl), and 2-propenyl. 1- (1-butenyl), 1- (2-butenyl), 1- (3-butenyl), 1- (1,3-butadienyl), 2- (2-butenyl), 1- (1-pentenyl) , 5- (cyclopentadienyl), 1- (1-cyclohexenyl) and the like.

Examples of the alkynyl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include ethynyl, propargyl (that is, 1- (2-propynyl)), 1- (1-propynyl), 1-butadiynyl. , 1- (1,3-pentadiynyl) and the like.

Examples of the aryl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include phenyl, o-tolyl (that is, 1- (2-methylphenyl)), m-tolyl, p-tolyl, 1- (2,3-dimethylphenyl), 1- (3,4-dimethylphenyl), 2- (1,3-dimethylphenyl), 1- (3,5-dimethylphenyl), 1- (2,5 -Dimethylphenyl), p-cumenyl, mesityl, 1-naphthyl, 2-naphthyl, 1-anthranyl, 2-anthranyl, 9-anthranyl, and 4-biphenylyl (ie, 1- (4-phenyl) phenyl), 3 -Biphenylyls such as biphenylyl, 2-biphenylyl, 4-p-terphenylyl (i.e. 1-4- (4-biphenylyl) phenyl), 4-m-terphenylyl (i.e. 1-4-4- , 3-biphenylyl) phenyl) terphenylyl such as and the like.

Examples of the heteroaryl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include a nitrogen atom, an oxygen atom, a sulfur atom, and the like as the hetero atom contained therein. Examples include imidazolyl, pyrazolyl, pyridyl, pyrazyl, pyrimidyl, triazinyl, quinolyl, isoquinolinyl, pyrrolyl, indolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl and the like.

Examples of the alkoxy group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include methoxy, ethoxy, isopropoxy, cyclopropoxy, n-butoxy, tert-butoxy, cyclohexyloxy and phenoxy. .

Examples of the acyl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include acetyl, benzoyl, formyl, pivaloyl and the like.

Examples of the acyloxy group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include acetoxy, benzoyloxy, and the like.

Examples of the amino group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino, pyrrolidino, piperidino, morpholino and the like. Can be mentioned.

Examples of the ester group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include methyl ester (that is, methoxycarbonyl), ethyl ester, isopropyl ester, phenyl ester, benzyl ester, and the like.

Examples of the amide group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include N, N-dimethylamide (that is, dimethylaminocarbonyl) and N-phenylamide linked by a carbon atom of the amide. N, N-diphenylamide, N-methylacetamide (that is, acetylmethylamino), N-phenylacetamide, N-phenylbenzamide and the like linked by a nitrogen atom of the amide.

Examples of the halogen represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the perfluoroalkyl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include trifluoromethyl, pentafluoroethyl, 1-perfluoropropyl, 2-perfluoropropyl, perfluoropentyl, and the like. Is mentioned.

Examples of the silyl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ include trimethylsilyl, triethylsilyl, triisopropylsilyl, triphenylsilyl, methyldiphenylsilyl, dimethylphenylsilyl, tert-butyldimethylsilyl. , Tert-butyldiphenylsilyl and the like.

Said R < ₁ > -R < ₄ > and X < ₁ > -X < ₁₂ > may be further substituted by another substituent. For example, examples of the alkyl group substituted with an aryl group include benzyl, 9-fluorenyl, 1- (2-phenylethyl), 1- (4-phenyl) cyclohexyl, etc., and the aryl group substituted with a heteroaryl group Examples thereof include 1- (4-N-carbazolyl) phenyl, 1- (3,5-di (N-carbazolyl)) phenyl, 1- (4- (2-pyridyl) phenyl) and the like.

R _{1 to} R ₄ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, an ester group, or a silyl group, and more preferably a hydrogen atom. , An alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, and a silyl group, and particularly preferably a hydrogen atom, an alkyl group, and an aryl group.

X _{1 to} X ₁₂ are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an amino group, an ester group, or a silyl group, and more preferably a hydrogen atom. , An alkyl group and an aryl group, particularly preferably a hydrogen atom.

The alkyl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n- Hexyl, cyclopentyl and cyclohexyl are more preferable, and methyl, ethyl, tert-butyl, n-hexyl and cyclohexyl are more preferable, and methyl and ethyl are particularly preferable.

The aryl group represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ is preferably phenyl, o-tolyl, 1- (3,4-dimethylphenyl), 1- (3,5-dimethylphenyl). , 1-naphthyl, 2-naphthyl, 9-anthranyl, and biphenylyls and terphenylyls, more preferably phenyl, biphenylyls, and terphenylyls, and more preferably phenyl.

The hydrogen atom represented by R _{1 to} R ₄ and X _{1 to} X ₁₂ may be a deuterium atom, and is preferably a deuterium atom.

  Part or all of the hydrogen atoms contained in the compound represented by the general formula (a) may be substituted with deuterium atoms.

At least one of R _{1 to} R ₄ is a double bond or a group having a triple bond. Examples of the double bond include C═C, C═O, C═S, C═N, N = N, S = O, P = O, etc., preferably C = C, C = O, C = N, S = O, P = O, more preferably C = C, C = O, C = N, particularly preferably C = C. Examples of the triple bond include C≡C and C≡N, and preferably C≡C.

As the group having a double bond or triple bond of R _{1 to} R ₄ , an aryl group is preferable, and among them, a phenyl group, a biphenylyl group, and a terphenylyl group represented by the following are preferable, and a phenyl group is particularly preferable.

At least one of R _{1 to} R ₄ is a group having a double bond or a triple bond, and the number of R _{1 to} R ₄ having a double bond or a triple bond is preferably 2 to 4. -4 is more preferable, and 4 is particularly preferable.

When the number of R _{1 to} R ₄ having a double bond or a triple bond is 1-3, R ^{1 to} R ⁴ consisting of only the remaining single bond is a hydrogen atom, an alkyl group, an alkoxy group or a silyl group. Preferably, a hydrogen atom, an alkyl group, and a silyl group are preferable, and a hydrogen atom and an alkyl group are particularly preferable.

R _{1 to} R ₄ and X _{1 to} X ₁₂ may be linked to each other to form a ring structure. For example, as described below, X ₂ , X ₃ and X ₉ may be linked to each other to form a diamantane structure, and X ₄ , X ₅ and X ₁₂ may be linked to each other to form a triamantane structure. May be formed. These diamantane structure and triamantane structure may be further substituted with a substituent.

  In the present invention, the compound represented by the general formula (a) is preferably mixed and contained. Preferably, compounds having different groups having a double bond or compounds having different numbers of substitutions can be used in combination. Examples of the group having a double bond include the above phenyl group, biphenylyl group, and terphenylyl group, and compounds having 1 to 4 substitutions thereof. For example, a mono-substituted product having a substitution number of 1 and a tetra-substitution product having a substitution number of 4 can be used.

  Specific examples of the compound represented by the general formula (a) used in the present invention are shown below, but the compound of the present invention is not limited thereto.

The compound represented by the general formula (a) can be synthesized by appropriately combining adamantane or a halogenated adamantane with an alkyl halide or an alkylmagnesium halide (Grignard reagent). For example, indium can be used to couple a halogenated adamantane and an alkyl halide (Reference 1). Alternatively, an alkyl halide can be converted into an alkyl copper reagent and coupled with an aromatic Grignard reagent (Reference 2). Alkyl halides can also be coupled using an appropriate aryl boric acid and a palladium catalyst (Reference 3).
Reference 1: Tetrahedron Lett. 39, 1998, 9557-9558.
Reference 2: Tetrahedron Lett. 39, 1998, 2095-2096.
Reference 3: J. Am. Chem. Soc. 124, 2002, 13662-13663.

  The adamantane skeleton having an aryl group can be synthesized by appropriately combining adamantane or a halogenated adamantane with the corresponding arene or aryl halide.

  In the production method shown above, when the defined substituent changes under the conditions of a certain synthesis method or is inappropriate for carrying out the method, the functional group is protected or deprotected (for example, Protective Groups in Organic Synthesis, by TW Greene, John Wiley & Sons Inc. (198) ) Etc.) and the like can be easily manufactured. Moreover, it is also possible to change the order of reaction steps such as introduction of substituents as necessary.

  The molecular weight of the compound represented by the general formula (a) is preferably 2000 or less from the viewpoint of vapor deposition suitability and solubility, since the organic electroluminescent device is prepared using a vacuum vapor deposition process or a solution coating process. It is more preferably 1200 or less, and particularly preferably 1000 or less. Further, from the viewpoint of vapor deposition suitability, if the molecular weight is too small, the vapor pressure becomes small, the change from the gas phase to the solid phase does not occur, and it is difficult to form an organic layer. Is more preferable, and 400 or more is particularly preferable.

  The compound represented by the general formula (a) is preferably used in combination with the compound represented by the general formula (I), and a platinum complex having a compound represented by the general formula (I) and a tetradentate ligand It is more preferable to use in combination.

  In the present invention, the compound represented by the general formula (a) is not limited in its use, and may be contained in any layer in the organic layer. As the introduction layer of the compound represented by the general formula (a), any one of a light emitting layer, a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an exciton block layer, and a charge block layer described later is used. It is preferable that the light-emitting layer, the hole injection layer, the hole transport layer, the electron transport layer, the electron injection layer, or the plurality of the light-emitting layer, It is particularly preferable to be contained in one or more of the hole injection layer and the hole transport layer, and most preferably used for the light emitting layer.

The content of the compound represented by the general formula (a) in the light emitting layer should be limited to an amount that does not suppress the charge transporting property of the charge transporting material, and the compound represented by the general formula (a) Is preferably contained in an amount of 0.1 to 70% by mass, more preferably 0.1 to 30% by mass, and particularly preferably 0.1 to 25% by mass.
Moreover, when using the compound represented by general formula (a) for a several organic layer, it is preferable to contain in said layer in each layer.

-Hole injection layer, hole transport layer-
The hole injection layer and the hole transport layer are layers having a function of receiving holes from the anode or the anode side and transporting them to the cathode side. Specifically, the hole injection layer and the hole transport layer are carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamines. Derivatives, amino-substituted chalcone derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, porphyrin compounds, organosilane derivatives, carbon, etc. Preferably there is.

  The thicknesses of the hole injection layer and the hole transport layer are each preferably 500 nm or less from the viewpoint of lowering the driving voltage.

  The thickness of the hole transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the hole injection layer is preferably 0.1 nm to 200 nm, more preferably 0.5 nm to 100 nm, and still more preferably 1 nm to 100 nm.

  The hole injection layer and the hole transport layer may have a single layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

-Electron injection layer, electron transport layer-
The electron injection layer and the electron transport layer are layers having a function of receiving electrons from the cathode or the cathode side and transporting them to the anode side. Specifically, the electron injection layer and the electron transport layer are triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, Carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, aromatic tetracarboxylic anhydrides such as naphthalene and perylene, phthalocyanine derivatives, 8-quinolinol derivative complexes, metal phthalocyanines, benzoxazoles and benzothiazoles as ligands It is preferably a layer containing various complexes typified by the complex to be prepared, an organosilane derivative, and the like.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 50 nm or less from the viewpoint of lowering the driving voltage.
The thickness of the electron transport layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm. In addition, the thickness of the electron injection layer is preferably 0.1 nm to 200 nm, more preferably 0.2 nm to 100 nm, and still more preferably 0.5 nm to 50 nm.
The electron injection layer and the electron transport layer may have a single-layer structure made of one or more of the materials described above, or may have a multilayer structure made up of a plurality of layers having the same composition or different compositions.

-Hole blocking layer-
The hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side. In the present invention, a hole blocking layer can be provided as an organic layer adjacent to the light emitting layer on the cathode side.
As an example of the organic compound constituting the hole blocking layer, aluminum (III) bis (2-methyl-8-quinolinato) 4-phenylphenolate (Aluminum (III) bis (2-methyl-8-quinolinato) 4- aluminum complexes such as phenylphenolate (abbreviated as BAlq), triazole derivatives, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (2,9-Dimethyl-4,7-diphenyl-1,10-) phenanthroline derivatives such as phenanthroline (abbreviated as BCP)) and the like.
The thickness of the hole blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
The hole blocking layer may have a single layer structure made of one or more of the materials described above, or may have a multilayer structure made of a plurality of layers having the same composition or different compositions.

<Protective layer>
In the present invention, the entire organic EL element may be protected by a protective layer.
As a material contained in the protective layer, any material may be used as long as it has a function of preventing materials that promote device deterioration such as moisture and oxygen from entering the device.
Specific examples thereof include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti, and Ni, MgO, SiO, SiO ₂ , Al ₂ O ₃ , GeO, NiO, CaO, BaO, and Fe ₂ O. ₃ , metal oxides such as Y ₂ O ₃ and TiO ₂ , metal nitrides such as SiN _x and SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ and CaF ₂ , polyethylene, polypropylene, polymethyl Monomer mixture containing methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene and at least one comonomer A copolymer obtained by copolymerization of a copolymer having a cyclic structure in the copolymer main chain. Copolymer, 1% by weight of the water absorbing water absorption material, water absorption of 0.1% or less of moisture-proof material, and the like.

  The method for forming the protective layer is not particularly limited, and for example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency) Excited ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, transfer method can be applied.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic layer. Specific examples include yttria-stabilized zirconia (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, and polycycloolefin. , Organic materials such as norbornene resin and poly (chlorotrifluoroethylene).

  For example, when glass is used as the substrate, alkali-free glass is preferably used as the material in order to reduce ions eluted from the glass. Moreover, when using soda-lime glass, it is preferable to use what gave barrier coatings, such as a silica. In the case of an organic material, it is preferable that it is excellent in heat resistance, dimensional stability, solvent resistance, electrical insulation, and workability.

  There is no restriction | limiting in particular about the shape of a board | substrate, a structure, a magnitude | size, It can select suitably according to the use, purpose, etc. of a light emitting element. In general, the shape of the substrate is preferably a plate shape. The structure of the substrate may be a single layer structure, a laminated structure, may be formed of a single member, or may be formed of two or more members.

  The substrate may be colorless and transparent or colored and transparent, but is preferably colorless and transparent in that it does not scatter or attenuate light emitted from the organic light emitting layer.

  The substrate can be provided with a moisture permeation preventing layer (gas barrier layer) on the front surface or the back surface.

  As a material for the moisture permeation preventive layer (gas barrier layer), inorganic materials such as silicon nitride and silicon oxide are preferably used. The moisture permeation preventing layer (gas barrier layer) can be formed by, for example, a high frequency sputtering method. When a thermoplastic substrate is used, a hard coat layer, an undercoat layer, or the like may be further provided as necessary.

<Anode>
The anode usually only needs to have a function as an electrode for supplying holes to the organic layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element, It can select suitably from well-known electrode materials. As described above, the anode is usually provided as a transparent anode.

  Suitable examples of the material for the anode include metals, alloys, metal oxides, conductive compounds, and mixtures thereof. Specific examples of the anode material include conductive metals such as tin oxide doped with antimony and fluorine (ATO, FTO), tin oxide, zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). Metals such as oxides, gold, silver, chromium, nickel, and mixtures or laminates of these metals and conductive metal oxides, inorganic conductive materials such as copper iodide and copper sulfide, polyaniline, polythiophene, polypyrrole, etc. Organic conductive materials, and a laminate of these and ITO. Among these, conductive metal oxides are preferable, and ITO is particularly preferable from the viewpoints of productivity, high conductivity, transparency, and the like.

  The anode is composed of, for example, a wet method such as a printing method and a coating method, a physical method such as a vacuum deposition method, a sputtering method, and an ion plating method, and a chemical method such as a CVD and a plasma CVD method. It can be formed on the substrate according to a method appropriately selected in consideration of suitability with the material to be processed. For example, when ITO is selected as the anode material, the anode can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.

  In the organic electroluminescent element of the present invention, the formation position of the anode is not particularly limited and can be appropriately selected according to the use and purpose of the light emitting element. Is preferably formed on the substrate. In this case, the anode may be formed on the entire one surface of the substrate, or may be formed on a part thereof.

  The patterning for forming the anode may be performed by chemical etching such as photolithography, or may be performed by physical etching such as laser, or vacuum deposition or sputtering with a mask overlapped. It may be performed by a lift-off method or a printing method.

  The thickness of the anode can be appropriately selected depending on the material constituting the anode and cannot be generally defined, but is usually about 10 nm to 50 μm, and preferably 50 nm to 20 μm.

The resistance value of the anode is preferably 10 ³ Ω / □ or less, and more preferably 10 ² Ω / □ or less. When the anode is transparent, it may be colorless and transparent or colored and transparent. In order to take out light emission from the transparent anode side, the transmittance is preferably 60% or more, and more preferably 70% or more.

  The transparent anode is detailed in Yutaka Sawada's “New Development of Transparent Conductive Film” published by CMC (1999), and the matters described here can be applied to the present invention. In the case of using a plastic substrate having low heat resistance, a transparent anode formed using ITO or IZO at a low temperature of 150 ° C. or lower is preferable.

<Cathode>
The cathode usually has a function as an electrode for injecting electrons into the organic layer, and there is no particular limitation on the shape, structure, size, etc., and it is known depending on the use and purpose of the light emitting device. The electrode material can be selected as appropriate.

  Examples of the material constituting the cathode include metals, alloys, metal oxides, electrically conductive compounds, and mixtures thereof. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium alloys, lithium-aluminum alloys, magnesium. -Rare earth metals such as silver alloys, indium, ytterbium, and the like. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection.

Among these, as a material constituting the cathode, an alkali metal or an alkaline earth metal is preferable from the viewpoint of electron injecting property, and a material mainly composed of aluminum is preferable from the viewpoint of excellent storage stability.
The material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01 to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy, etc.) Say.

  The cathode materials are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these publications can also be applied in the present invention.

  There is no restriction | limiting in particular about the formation method of a cathode, According to a well-known method, it can carry out. For example, the cathode described above is configured from a wet method such as a printing method or a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method. It can be formed according to a method appropriately selected in consideration of suitability with the material. For example, when a metal or the like is selected as the cathode material, one or more of them can be simultaneously or sequentially performed according to a sputtering method or the like.

  Patterning when forming the cathode may be performed by chemical etching such as photolithography, physical etching by laser, or the like, or by vacuum deposition or sputtering with the mask overlaid. It may be performed by a lift-off method or a printing method.

In the present invention, the cathode forming position is not particularly limited, and may be formed on the entire organic layer or a part thereof.
Further, a dielectric layer made of an alkali metal or alkaline earth metal fluoride or oxide may be inserted between the cathode and the organic layer with a thickness of 0.1 to 5 nm. This dielectric layer can also be regarded as a kind of electron injection layer. The dielectric layer can be formed by, for example, a vacuum deposition method, a sputtering method, an ion plating method, or the like.

The thickness of the cathode can be appropriately selected depending on the material constituting the cathode and cannot be generally defined, but is usually about 10 nm to 5 μm, and preferably 50 nm to 1 μm.
Further, the cathode may be transparent or opaque. The transparent cathode can be formed by depositing a thin cathode material to a thickness of 1 to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

<Sealing container>
The element of this invention may seal the whole element using a sealing container. You may enclose a water | moisture-content absorber or an inert liquid in the space between a sealing container and an element. Although it does not specifically limit as a moisture absorber, For example, barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide, calcium chloride, magnesium chloride, copper chloride Cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, magnesium oxide and the like. The inert liquid is not particularly limited, and examples thereof include fluorinated solvents such as paraffins, liquid paraffins, perfluoroalkanes, perfluoroamines, perfluoroethers, chlorinated solvents, and silicone oils. It is done.

  The element of the present invention can obtain light emission by applying a direct current (which may include an alternating current component if necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. it can.

<Driving method>
Regarding the driving method of the element of the present invention, JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234665, and JP-A-8-214447, The driving methods described in Japanese Patent No. 2784615, US Pat. Nos. 5,828,429 and 6023308, etc. can be applied.

<Others>
The external quantum efficiency of the light emitting device of the present invention is preferably 5% or more, and more preferably 7% or more. The value of the external quantum efficiency should be the maximum value of the external quantum efficiency when the device is driven at 20 ° C., or the value of the external quantum efficiency near 100 to 300 cd / m ² when the device is driven at 20 ° C. Can do.

  The internal quantum efficiency of the light emitting device of the present invention is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. The internal quantum efficiency of the device is calculated by dividing the external quantum efficiency by the light extraction efficiency. In a normal organic EL element, the light extraction efficiency is about 20%. However, the shape of the substrate, the shape of the electrode, the thickness of the organic layer, the thickness of the inorganic layer, the refractive index of the organic layer, the refractive index of the inorganic layer, etc. By devising it, it is possible to increase the light extraction efficiency to 20% or more.

  The light emitting device of the present invention preferably has a maximum intensity wavelength of an emission spectrum at 350 nm to 700 nm, more preferably 350 nm to 600 nm, still more preferably 400 to 550 nm, and particularly preferably 430 to 500 nm.

  The element of the present invention can be suitably used for display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

  Hereinafter, the present invention will be described in detail based on examples, but the embodiment of the present invention is not limited thereto.

(Example 1-1)
A glass substrate having an ITO film of 0.5 mm thickness and 2.5 cm square (manufactured by Geomatek Co., Ltd., surface resistance 10 Ω / □) is placed in a cleaning container, ultrasonically cleaned in 2-propanol, and then treated with UV-ozone for 30 minutes. Went. The following organic layers (organic compound layers) were sequentially deposited on the transparent anode (ITO film) by vacuum deposition.
The vapor deposition rate in the examples of the present invention is 0.2 nm / second unless otherwise specified. The deposition rate was measured using a quartz resonator. The film thicknesses described below were also measured using a crystal resonator.

  The cleaned ITO substrate was put into a vapor deposition apparatus, copper phthalocyanine was vapor-deposited 10 nm (first layer), and HT-1 was vapor-deposited thereon 40 nm (second layer). On top of this, H-1 and the compound (1) of the present invention were vapor-deposited at a ratio of 95: 5 (mass ratio) of 50 nm (third layer / light-emitting layer), and ET-1 was vapor-deposited thereon at 40 nm ( 4th layer). On top of this, 3 nm of lithium fluoride was deposited, and then 60 nm of aluminum was deposited. Without exposing it to the atmosphere, put it in a glove box substituted with argon gas, and seal it using a stainless steel sealing can and an ultraviolet curable adhesive (XNR5516HV, manufactured by Nagase Ciba Co., Ltd.) The organic EL element of Example 1-1 was produced. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (1) of the present invention was obtained.

(Example 1-2)
In Example 1-1, Example 1 was used except that Compound (2) of the present invention was used instead of Compound (1) of the present invention, and H-4 was used instead of H-1. Thus, an organic EL device of Example 1-2 was produced. As a result of emitting light by applying a DC constant voltage to the organic EL device using a source measure unit 2400 type manufactured by Toyo Technica, green light emission derived from the compound (2) of the present invention was obtained.

(Example 1-3)
In Example 1-1, Example 1 was used except that Compound (3) of the present invention was used instead of Compound (1) of the present invention, and H-3 was used instead of H-1. Thus, an organic EL device of Example 1-3 was produced. As a result of emitting light by applying a DC constant voltage to the organic EL element using a source measure unit 2400 type manufactured by Toyo Technica, green light emission derived from the compound (3) of the present invention was obtained.

(Example 1-4)
Example 1-3 is the same as Example 1-1 except that compound (4) of the present invention was used instead of compound (3) of the present invention, and HT-2 was used instead of HT-1. Thus, an organic EL device of Example 1-4 was produced. As a result of emitting light by applying a DC constant voltage to the organic EL element using a source measure unit 2400 type manufactured by Toyo Technica, green light emission derived from the compound (4) of the present invention was obtained.

(Example 1-5)
Example 1-1 is the same as Example 1-1 except that compound (5) of the present invention was used instead of compound (1) of the present invention, and H-6 was used instead of H-1. Thus, an organic EL device of Example 1-5 was produced. As a result of emitting light by applying a DC constant voltage to the organic EL element using a source measure unit 2400 type manufactured by Toyo Technica, red light emission derived from the compound (5) of the present invention was obtained.

(Example 1-6)
In Example 1-5, an organic EL device of Example 1-6 was produced in the same manner as in Example 1-5, except that H-7 was used instead of H-6. As a result of emitting light by applying a DC constant voltage to the organic EL element using a source measure unit 2400 type manufactured by Toyo Technica, red light emission derived from the compound (5) of the present invention was obtained.

(Example 1-7)
In Example 1-5, an organic EL device of Example 1-7 was produced in the same manner as in Example 1-5, except that H-2 was used instead of H-6. As a result of emitting light by applying a DC constant voltage to the organic EL element using a source measure unit 2400 type manufactured by Toyo Technica, red light emission derived from the compound (5) of the present invention was obtained.

(Example 1-8)
Example 1-1 is the same as Example 1-1 except that compound (6) of the present invention was used instead of compound (1) of the present invention, and HT-2 was used instead of HT-1. Thus, an organic EL device of Example 1-8 was produced. As a result of emitting light by applying a DC constant voltage to the organic EL element using a source measure unit 2400 type manufactured by Toyo Technica, green light emission derived from the compound (6) of the present invention was obtained.

(Example 1-9)
Example 1-1 is the same as Example 1-1 except that compound (7) of the present invention was used instead of compound (1) of the present invention, and H-5 was used instead of H-1. Thus, an organic EL device of Example 1-9 was produced. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (7) of the present invention was obtained.

(Example 1-10)
In Example 1-1, an organic EL device of Example 1-10 was produced in the same manner as Example 1-1 except that Compound (8) of the present invention was used instead of Compound (1) of the present invention. did. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (8) of the present invention was obtained.

(Example 1-11)
Example 1-9 was the same as Example 1-9 except that compound (9) of the present invention was used instead of compound (7) of the present invention, and HT-2 was used instead of HT-1. Thus, an organic EL device of Example 1-11 was produced. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (9) of the present invention was obtained.

(Example 1-12)
In Example 1-1, an organic EL device of Example 1-12 was produced in the same manner as Example 1-1 except that Compound (10) of the present invention was used instead of Compound (1) of the present invention. did. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (10) of the present invention was obtained.

(Example 1-13)
In Example 1-1, an organic EL device of Example 1-13 was produced in the same manner as Example 1-1 except that Compound (11) of the present invention was used instead of Compound (1) of the present invention. did. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (11) of the present invention was obtained.

(Example 1-14)
In Example 1-1, an organic EL device of Example 1-14 was produced in the same manner as in Example 1-1 except that H-2 was used instead of H-1. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (1) of the present invention was obtained.

(Example 1-15)
In Example 1-9, an organic EL device of Example 1-15 was produced in the same manner as in Example 1-9, except that H-2 was used instead of H-5. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (7) of the present invention was obtained.

(Example 1-16)
In Example 1-12, an organic EL device of Example 1-16 was produced in the same manner as in Example 1-12, except that H-2 was used instead of H-1. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (10) of the present invention was obtained.

(Example 1-17)
In Example 1-1, an organic EL device of Example 1-17 was produced in the same manner as Example 1-1 except that Compound (12) of the present invention was used instead of Compound (1) of the present invention. did. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (12) of the present invention was obtained.

(Example 1-18)
Example 1-1 is the same as Example 1-1 except that the compound (13) of the present invention was used instead of the compound (1) of the present invention, and H-5 was used instead of H-1. Thus, an organic EL device of Example 1-18 was produced. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (13) of the present invention was obtained.

(Example 1-19)
In Example 1-1, an organic EL device of Example 1-19 was produced in the same manner as Example 1-1 except that Compound (14) of the present invention was used instead of Compound (1) of the present invention. did. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (14) of the present invention was obtained.

(Example 1-20)
In Example 1-1, an organic EL device of Example 1-20 was produced in the same manner as Example 1-1 except that Compound (15) of the present invention was used instead of Compound (1) of the present invention. did. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (15) of the present invention was obtained.

(Example 1-21)
Example 1-1 is the same as Example 1-1 except that compound (16) of the present invention was used instead of compound (1) of the present invention, and H-5 was used instead of H-1. Thus, an organic EL device of Example 1-21 was produced. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (16) of the present invention was obtained.

(Example 1-22)
In Example 1-17, the organic EL element of Example 1-22 was produced like Example 1-17 except having used H-2 instead of H-1. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (12) of the present invention was obtained.

(Example 1-23)
In Example 1-18, an organic EL device of Example 1-23 was produced in the same manner as in Example 1-18, except that H-2 was used instead of H-5. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (13) of the present invention was obtained.

(Example 1-24)
In Example 1-19, an organic EL device of Example 1-24 was produced in the same manner as in Example 1-19 except that H-2 was used instead of H-1. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (14) of the present invention was obtained.

(Comparative Example 1-1)
In Example 1-1, the organic EL device of Comparative Example 1-1 was used in the same manner as Example 1-1 except that the compound described in JP-A-2006-261623 was used instead of the compound (1) of the present invention. Was made. As a result of applying a direct current constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, green light emission derived from the compound described in JP-A-2006-261623 was obtained.

(Comparative Example 1-2)
In Example 1-1, the organic EL device of Comparative Example 1-2 was used in the same manner as Example 1-1 except that the compound described in JP-A-2008-37848 was used instead of the compound (1) of the present invention. Was made. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, green light emission derived from the compound described in JP-A-2008-37848 was obtained.

(Measurement of drive voltage)
The organic electroluminescent elements of Examples 1-1 to 1-24, Comparative Example 1-1, and Comparative Example 1-2 were set in an emission spectrum measurement system (ELS1500) manufactured by Shimadzu Corporation, and their luminance was The applied voltage at 100 cd / m ² was measured.

(Driving durability evaluation)
The organic electroluminescent elements of Examples 1-1 to 1-24, Comparative Example 1-1, and Comparative Example 1-2 were set in an OLED test system ST-D type manufactured by Tokyo System Development Co., Ltd. The device was driven under the condition of an initial luminance of 1000 cd / m ^{2 in} the mode, and the luminance half time was measured.

(Evaluation of external quantum efficiency)
The organic electroluminescent elements of Examples 1-1 to 1-24, Comparative Example 1-1, and Comparative Example 1-2 were applied with a DC constant voltage to the EL element using a source measure unit 2400 type manufactured by Toyo Technica. Was emitted. The external quantum efficiency (%) was calculated from the front luminance at 100 cd / m ² .

In Examples 1-1 to 1-24, by using the compound represented by the general formula (I) as a luminescent material, the luminance half-life is longer than those of Comparative Examples 1 and 2, and the durability is thereby improved. It turns out that it is excellent.
Moreover, it turns out that Examples 1-6-7, 14-16, 22-24 using the material which has at least 1 deuterium atom have a long brightness | luminance half-life, and are further excellent in durability. Similarly, a light-emitting element having excellent light-emitting performance can be manufactured using other compounds of the present invention.

(Example 2-1)

  In Example 1-1, the composition ratio of the film of the third layer (light emitting layer) is H-1 and the compound (1) of the present invention is 95: 5 (mass ratio), and H-1, A-1, An organic EL device of Example 2-1 was produced in the same manner as in Example 1-1, except that the compound (1) of the invention was changed to 80: 15: 5 (mass ratio) and deposited (film thickness: 50 nm). . As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (1) of the present invention was obtained.

(Example 2-2)
In Example 2-1, the compound (7) of the present invention was used instead of the compound (1) of the present invention, H-5 was used instead of H-1, and A- An organic EL device of Example 2-2 was produced in the same manner as in Example 2-1, except that 2. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (7) of the present invention was obtained.

(Example 2-3)
Example 2-1 was the same as Example 2-1 except that compound (10) of the present invention was used instead of compound (1) of the present invention, and A-2 was used instead of A-1. Thus, an organic EL device of Example 2-3 was produced. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (10) of the present invention was obtained.

(Example 2-4)
Example 2-1 was the same as Example 2-1 except that compound (12) of the present invention was used instead of compound (1) of the present invention, and A-2 was used instead of A-1. Thus, an organic EL device of Example 2-4 was produced. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (12) of the present invention was obtained.

(Example 2-5)
Example 2-1 was the same as Example 2-1 except that compound (13) of the present invention was used instead of compound (1) of the present invention, and H-5 was used instead of H-1. Thus, an organic EL device of Example 2-5 was produced. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (13) of the present invention was obtained.

(Example 2-6)
In Example 2-1, the compound (14) of the present invention was used instead of the compound (1) of the present invention, and A-2 was used instead of A-1, as in Example 2-1. Thus, an organic EL device of Example 2-6 was produced. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (14) of the present invention was obtained.

(Example 2-7)
In Example 2-1, an organic EL device of Example 2-7 was produced in the same manner as in Example 2-1, except that H-2 was used instead of H-1. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (1) of the present invention was obtained.

(Example 2-8)
In Example 2-2, an organic EL element of Example 2-8 was produced in the same manner as in Example 2-2 except that H-2 was used instead of H-5. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (7) of the present invention was obtained.

(Example 2-9)
In Example 2-3, an organic EL element of Example 2-9 was produced in the same manner as Example 2-3 except that H-2 was used instead of H-1. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (10) of the present invention was obtained.

(Example 2-10)
In Example 2-4, an organic EL device of Example 2-10 was produced in the same manner as in Example 2-4 except that H-2 was used instead of H-1. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit 2400 type manufactured by Toyo Technica, blue-white light emission derived from the compound (12) of the present invention was obtained.

(Example 2-11)
In Example 2-5, an organic EL device of Example 2-11 was produced in the same manner as in Example 2-5 except that H-2 was used instead of H-5. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (13) of the present invention was obtained.

(Example 2-12)
In Example 2-6, an organic EL element of Example 2-12 was produced in the same manner as in Example 2-6, except that H-2 was used instead of H-1. As a result of applying a constant DC voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, blue-white light emission derived from the compound (14) of the present invention was obtained.

(Comparative Example 2-1)
In Example 2-1, the organic EL device of Comparative Example 2-1 was used in the same manner as in Example 2-1, except that the compound described in JP-A-2006-261623 was used instead of the compound (1) of the present invention. Was made. As a result of applying a direct current constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, green light emission derived from the compound described in JP-A-2006-261623 was obtained.

(Comparative Example 2-2)
In Example 2-1, Example 2-1 was used except that the compound described in JP-A-2008-37848 was used instead of compound (1) of the present invention, and A-2 was used instead of A-1. In the same manner, an organic EL device of Comparative Example 2-2 was produced. As a result of applying a DC constant voltage to the organic EL element to emit light using a source measure unit type 2400 manufactured by Toyo Technica, green light emission derived from the compound described in JP-A-2008-37848 was obtained.

(Measurement of drive voltage)
The organic electroluminescent elements of Examples 2-1 to 2-12, Comparative Example 2-1 and Comparative Example 2-2 were set in an emission spectrum measurement system (ELS1500) manufactured by Shimadzu Corporation, and their luminance was The applied voltage at 100 cd / m ² was measured.

(Driving durability evaluation)
The organic electroluminescent elements of Examples 2-1 to 2-12, Comparative Example 2-1 and Comparative Example 2-2 were set in an OLED test system ST-D type manufactured by Tokyo System Development Co., Ltd. The device was driven under the condition of an initial luminance of 1000 cd / m ^{2 in} the mode, and the luminance half time was measured.

(Evaluation of external quantum efficiency)
The organic electroluminescent elements of Examples 2-1 to 2-12, Comparative Example 2-1 and Comparative Example 2-2 were applied with a constant DC voltage to the EL element using a source measure unit 2400 type manufactured by Toyo Technica. Was emitted. The external quantum efficiency (%) was calculated from the front luminance at 100 cd / m ² .

  The above Examples 2-1 to 2-12 are replaced with Example 1-1, Example 1-9, Example 1-12, Example 1-17 to 1-19, Example 1-22 to Example 1-24. In comparison with Comparative Examples 2-1 and 2-2, the device in which the compound represented by the general formula (I) and the compound represented by the general formula (a) are combined has a long luminance half-life and is durable. It turns out that it is excellent in terms. Similarly, a light-emitting element having excellent light-emitting performance can be manufactured using other compounds of the present invention.

Claims (9)

An organic electroluminescent element having at least one organic layer including a light emitting layer between a pair of electrodes, wherein the organic electroluminescent element contains at least one compound represented by the following general formula (I) in at least one organic layer element.

In the general formula (I), X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , and X ⁸ represents a nitrogen atom. X ¹ , X ² , X ³ , X ⁴ , X ⁵ , X ⁶ , X ⁷ , X ⁸ , X ¹¹ , X ¹² , X ¹³ , X ¹⁴ , and X ¹⁵ are each independently substituted if further replaceable It may have a group. M represents a divalent metal ion. L ¹ represents a divalent linking group. A broken line representing a bond between a metal and a nitrogen atom represents a coordination bond, and a solid line representing a bond between the metal and a carbon atom represents a covalent bond. The organic electroluminescent element according to claim 1, wherein the general formula (I) is represented by the following general formula (II).

In the general formula (II), X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , and X ²⁸ represents a nitrogen atom. X ²¹ , X ²² , X ²³ , X ²⁴ , X ²⁵ , X ²⁶ , X ²⁷ , X ²⁸ , X ³¹ , X ³² , X ³³ , X ³⁴ , and X ³⁵ are each independently substituted if further replaceable It may have a group. L ² represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond. The organic electroluminescent element according to claim 2, wherein the general formula (II) is represented by the following general formula (III).

In the general formula (III), X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently Represents an atom selected from carbon or nitrogen, and any one of X ⁴¹ , X ⁴² , X ⁴³ , and X ⁴⁴ represents a nitrogen atom. X ⁴¹ , X ⁴² , X ⁴³ , X ⁴⁴ , X ⁴⁵ , X ⁴⁶ , X ⁴⁷ , X ⁴⁸ , X ⁵¹ , X ⁵² , X ⁵³ , X ⁵⁴ , and X ⁵⁵ are each independently substituted if further replaceable It may have a group. L ³ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond. The organic electroluminescence device according to claim 3, wherein the general formula (III) is represented by the following general formula (IV).

In the general formula ^{(IV), X 61, X} 62, X 63, X 64, X 65, X 66, X 67, and X ⁶⁸ represents an atom selected from carbon or nitrogen independently, X ^61, Any one of X ⁶² , X ⁶³ and X ⁶⁴ represents a nitrogen atom. When X ⁶¹ , X ⁶² , X ⁶³ , X ⁶⁴ , X ⁶⁵ , X ⁶⁶ , X ⁶⁷ , and X ⁶⁸ can be further substituted, each may independently have a substituent. R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ , and R ⁶⁵ each independently represent a hydrogen atom or a substituent. L ⁴ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond. The organic electroluminescent element according to claim 4, wherein the general formula (IV) is represented by the following general formula (V).

In the general formula (V), X ⁷¹ , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , X ⁷⁷ , and X ⁷⁸ each independently represent an atom selected from carbon or nitrogen. When X ⁷¹ , X ⁷³ , X ⁷⁴ , X ⁷⁵ , X ⁷⁶ , X ⁷⁷ , and X ⁷⁸ can be further substituted, each may independently have a substituent. R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , and R ⁷⁵ each independently represent a hydrogen atom or a substituent. L ⁵ represents a divalent linking group. A broken line representing a bond between a platinum atom and a nitrogen atom represents a coordination bond, and a solid line representing a bond between a platinum atom and a carbon atom represents a covalent bond.   Furthermore, the organic electroluminescent element in any one of the Claims 1-5 which contain the material which has at least 1 deuterium atom in either of an organic layer.   Furthermore, the light emitting layer contains the material which has at least 1 deuterium atom, The organic electroluminescent element in any one of Claims 1-5 characterized by the above-mentioned.   The organic electroluminescent device according to claim 1, wherein the material having at least one deuterium atom is a material including a carbazole skeleton or an indole skeleton having at least one deuterium atom. Furthermore, the compound represented by the following general formula (a) is included in a light emitting layer, The organic electroluminescent element in any one of Claims 1-8 characterized by the above-mentioned.

In the general formula (a), R _{1 to} R ₄ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an acyl group, an acyloxy group, an amino group, a nitro group, Represents a group, a cyano group, an ester group, an amide group, a halogen group, a perfluoroalkyl group, or a silyl group, and at least one of R _{1 to} R ₄ is a group having a double bond or a triple bond. X _{1 to} X ₁₂ are each independently a hydrogen atom, alkyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, acyl group, acyloxy group, amino group, nitro group, cyano group, ester group, amide group Represents a halogen group, a perfluoroalkyl group, or a silyl group.