JP4703139B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescent element capable of emitting light by converting electric energy into light.

  Today, research and development on various display elements are active. Among them, organic electroluminescence (EL) elements are attracting attention as promising display elements because they can emit light with high luminance at a low voltage.

As a means for improving the EL device characteristics, a green light-emitting device using light emission from a triplet state of an ortho-metalated iridium complex (Ir (ppy) ₃ : Tris-Ortho-Metalated Complex of Iridium (III) with 2-Phenylpyridine)) Has been reported (Non-patent Document 1). This device has achieved an external quantum yield of 8%, which exceeds the external quantum yield of 5%, which was said to be the limit of conventional devices, but is limited to green light emission. There has been a demand for the development of light-emitting elements that are narrow, highly efficient, and in other colors.
In particular, improvement of device durability has recently been demanded. However, in devices using this triplet light emitting material, low device durability is a big problem, and it has been demanded to improve this.

  Various aromatic fused hydrocarbon materials have been proposed as a suitable means for improving the durability of the element. For example, Patent Documents 1 and 2 disclose diphenylanthracene derivatives.

However, the aromatic fused ring material as described above has a low energy level of T ₁ and is disadvantageous in terms of energy transfer efficiency with respect to the dopant when used as a host material of a triplet light emitting device. In order to improve luminous efficiency, it has been desired to develop an aromatic fused ring material having a higher T ₁ energy level.

On the other hand, since triphenylene has a high T ₁ level, it is a particularly useful skeleton for a host material of a triplet light emitting device.
As examples of using a compound having a triphenylene skeleton in a triplet light emitting device, Patent Documents 3 and 4 disclose devices using a liquid crystalline compound having a triphenylene structure. In the said invention, it is reported that luminous efficiency improves by making the light emitting layer express the liquid crystallinity derived from a triphenylene compound.

  However, in the invention disclosed herein, since the light emitting layer containing a compound having a triphenylene structure has liquid crystallinity, it is greatly affected by thermal vibration as compared with a light emitting element by a normal solid film, and in terms of element durability. Further improvements are desired.

JP-A-8-12600 JP 2001-335516 A JP 2002-43056 A US2002 / 0038860A1 Applied Physics Letters, 75, 4 (1999).

  An object of the present invention is to provide an organic EL light emitting device having good light emission characteristics and device driving durability.

（式中、Ｍ^１１、Ｍ^２１はそれぞれ独立に金属イオンを表し、Ｌ^１１、Ｌ^２１はそれぞれ独立に配位子を表す。Ｘ^１１、Ｘ^２１はそれぞれ独立に酸素原子、置換または無置換の窒素原子、硫黄原子を表し、Ｑ^１１、Ｑ^２１はそれぞれ独立に芳香環を形成する原子群を表す。Ｑ^１２、Ｑ^２２はそれぞれ独立に含窒素芳香環を形成する原子群を表す。ｍ^１１、ｍ^２１はそれぞれ独立に０〜３の整数を表し、ｍ^１２、ｍ^２２はそれぞれ独立に１〜４の整数を表す。）
（３）前記の一般式（１）の連結基Ｌが、単結合又は下記の基のいずれか１つの基である（１）又は（２）に記載の有機電界発光素子。

（４）前記一般式（１）で示される化合物が下記一般式（１Ａ）で示される化合物であることを特徴とする（１）又は（２）に記載の有機電界発光素子。

（式中、Ｔ¹はそれぞれ同じでも異なっていても良い、置換基を有していてもよいトリフェニレンを含む基を表し、Ar¹はそれぞれ同じでも異なっていても良いアルキル基、アリール基、ヘテロアリール基を表す。ｐは２以上４以下の整数を表す。）
（５）前記一般式（１）で表わされる化合物が下記一般式（１Ｂ）で示される化合物であることを特徴とする（１）又は（２）に記載の有機電界発光素子。

（式中、Ｔ²はそれぞれ同じでも異なっていても良い、置換基を有していてもよいトリフェニレンを含む基を表し、Ａｒ²はそれぞれ同じでも異なっていても良いアルキル基、アリール基、ヘテロアリール基を表す。Ｌ²はアリーレン基又はヘテロアリーレン基である２価以上６価以下の連結基を表し、qは２以上６以下の整数を表す。）
（６）一般式（１Ａ）で表される化合物。

（式中、Ｔ¹はそれぞれ同じでも異なっていても良い、置換基を有していてもよいトリフェニレンを含む基を表し、Ar¹はそれぞれ同じでも異なっていても良いアルキル基、アリール基、ヘテロアリール基を表す。ｐは２以上４以下の整数を表す。）
（７）一般式（１Ｂ）で表される化合物。

（式中、Ｔ²はそれぞれ同じでも異なっていても良い、置換基を有していてもよいトリフェニレンを含む基を表し、Ａｒ²はそれぞれ同じでも異なっていても良いアルキル基、アリール基、ヘテロアリール基を表す。Ｌ²はアリーレン基又はヘテロアリーレン基である２価以上６価以下の連結基を表し、qは２以上６以下の整数を表す。）
（８）前記一般式（１Ａ）または一般式（１Ｂ）で表わされる、有機電界発光素子用ホスト材料。 This object has been achieved 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, and comprising a compound represented by the following general formula (1), a host material for a phosphorescent material (A ) And at least one phosphorescent material, and utilizes phosphorescence emission from a triplet excited state of the light emitting material.
General formula (1) LT _n
(In the formula, L represents a single bond or a linking group composed of a divalent to octavalent aromatic ring, a divalent to octavalent aromatic heterocyclic ring, a carbon atom, a nitrogen atom or a silicon atom, and T has a substituent. And n represents an integer of 2 to 8, and T may be independently different or the same.)
(2) The light emitting layer of the light emitting device according to (1) further contains a compound represented by the following general formula (2) or general formula (3) as the metal complex host material (B). Organic electroluminescent device.

(In the formula, M ¹¹ and M ²¹ each independently represent a metal ion, and L ¹¹ and L ²¹ each independently represent a ligand. X ¹¹ and X ²¹ are each independently an oxygen atom, substituted or unsubstituted. nitrogen atom, a sulfur ^atom, a ^{Q 11, Q 21 .Q 12,} Q 22 is an atomic group forming a nitrogen-containing aromatic ring each independently representing an atomic group forming an aromatic ring each independently ^{.m 11} And m ²¹ each independently represents an integer of 0 to 3, and m ¹² and m ²² each independently represents an integer of 1 to 4.)
(3) The organic electroluminescent element according to (1) or (2), wherein the linking group L of the general formula (1) is a single bond or any one of the following groups .

(4) The organic electroluminescent element as described in (1) or (2), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1A).

(In the formula, each T ¹ may be the same or different, and represents a group containing triphenylene which may have a substituent, and Ar ¹ may be the same or different from each other, an alkyl group, an aryl group, or a hetero group. Represents an aryl group, and p represents an integer of 2 or more and 4 or less.)
(5) The organic electroluminescent element as described in (1) or (2), wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1B).

(In the formula, each T ² may be the same or different, and represents a group containing triphenylene which may have a substituent, and Ar ² may be the same or different from each other, an alkyl group, an aryl group, or a hetero group. .L ² representing the aryl group represents a divalent or higher hexavalent following linking group is an arylene group or a heteroarylene group, q is an integer of 2 to 6.)
(6) A compound represented by the general formula (1A).

(In the formula, each T ¹ may be the same or different, and represents a group containing triphenylene which may have a substituent, and Ar ¹ may be the same or different from each other, an alkyl group, an aryl group, or a hetero group. Represents an aryl group, and p represents an integer of 2 or more and 4 or less.)
(7) A compound represented by the general formula (1B).

(In the formula, each T ² may be the same or different, and represents a group containing triphenylene which may have a substituent, and Ar ² may be the same or different from each other, an alkyl group, an aryl group, or a hetero group. .L ² representing the aryl group represents a divalent or higher hexavalent following linking group is an arylene group or a heteroarylene group, q is an integer of 2 to 6.)
(8) A host material for an organic electroluminescent element represented by the general formula (1A) or the general formula (1B).

  The light emitting device of the present invention is excellent in light emitting characteristics and durability.

The present invention provides a light-emitting element having a light-emitting layer or a plurality of organic compound layers including a light-emitting layer between a pair of electrodes, including at least one host material (A) having at least two triphenylene structures, and further from a triplet excited state. It is related with the organic electroluminescent element characterized by utilizing light emission of this.
The host material (A) may be contained in any of the organic layers, but is preferably contained in the hole transport layer or the light emitting layer.

  Luminescence from the triplet excited state is synonymous with phosphorescence, and materials that emit phosphorescence will be described as phosphorescent materials in the future. Although it does not specifically limit as a phosphorescent material, A transition metal complex is preferable. The central metal of the transition metal complex is not particularly limited, but iridium, platinum, rhenium and ruthenium are preferable, iridium and platinum are more preferable, and iridium is further preferable.

  Moreover, as a transition metal complex, an ortho metalation complex is preferable. Orthometalated complexes are, for example, “Organic Metal Chemistry-Fundamentals and Applications” p150, 232 Akafusa Yamamoto, published by Akio Yamamoto, 1982, and “Photochemistry and Photophysics of Coordination Compounds” p71-p77, p135. -p146 A general term for a group of compounds described in Springer-Verlag H. Yersin published in 1987.

  The phosphorescent material used in the present invention is preferably a material having a phosphorescence quantum yield of 70% or more at 20 ° C., more preferably a material having a phosphorescence quantum yield of 20% or more at 20 ° C., and a phosphorescence quantum at 20 ° C. A material having a yield of 85% or more is more preferable.

  In the light emitting device of the present invention, a layer containing a compound having an ionization potential of 5.9 eV or more (more preferably 6.0 eV or more) is preferably used between the cathode and the light emitting layer, and an electron transport layer having an ionization potential of 5.9 eV or more is used. Is more preferable.

  In the light emitting device of the present invention, from the viewpoint of color purity, the half width of the emission spectrum is preferably 100 nm or less, more preferably 90 nm or less, further preferably 80 nm or less, and particularly preferably 70 nm or less.

The host material (A) will be described. The host material (A) is a compound that includes a group having triphenylene ( triphenylene structure ) and does not exhibit liquid crystallinity.
The triphenylene structure contained in the host material may have a substituent. Examples of the substituent include an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 carbon atom). -10, for example, methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like, and an alkenyl group (preferably having a carbon number). 2 to 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl.

Alkynyl group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as propargyl, 3-pentynyl, etc.), aryl group (preferably carbon Number 6 to 30, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, naphthyl, anthranyl, etc.), amino group (preferably carbon number) 0 to 30, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 10 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino). Alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably carbon Is a number from 1 to 10, for example methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like.),

An aryloxy 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 phenyloxy, 1-naphthyloxy, 2-naphthyloxy and the like. ), A heteroaryloxy 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 pyridyloxy, pyrazyloxy, pyrimidyloxy and quinolyloxy). 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 2-30 carbon atoms, more preferably 2-20 carbon atoms, particularly preferably A prime number of 2 to 12, for example, methoxycarbonyl, ethoxycarbonyl, etc.), an aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 12 carbon atoms). Such as phenyloxycarbonyl).

An acyloxy group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), an acylamino group (preferably having a carbon number) 2 to 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkoxycarbonylamino group (preferably 2 to 30 carbon atoms, More preferably, it has 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, and aryloxycarbonylamino group (preferably 7 to 30 carbon atoms, more preferably carbon atoms). 7 to 20, particularly preferably 7 to 12 carbon atoms, for example phenyloxycarbonylamino ), Sulfonylamino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc. ),

A sulfamoyl group (preferably having 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 12 carbon atoms, such as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc. ), A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc. ), An alkylthio 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). Has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, Preferably it is C6-C12, for example, phenylthio etc. are mentioned), heteroarylthio group (preferably C1-C30, more preferably C1-C20, especially preferably C1-C12. Yes, for example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 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 Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group Group,

Heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl and furyl. , Thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl group, azepinyl group, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, especially Preferably, it has 3 to 24 carbon atoms, and examples thereof include trimethylsilyl, triphenylsilyl and the like. These substituents may be further substituted and may combine with each other to form a ring.

  The substituent that the triphenylene structure contained in the host material (A) may have is preferably an alkyl group, an aryl group, or a heteroaryl group, more preferably a phenyl group or a biphenyl group.

  The host material (A) may be a low molecular compound, and an oligomer compound or a polymer compound (weight average molecular weight (polystyrene conversion) is preferably 1000 to 5000000, more preferably 2000 to 1000000, still more preferably 3000 to 100000. It may be. In the case of a polymer compound, a triphenylene structure may be contained in the polymer main chain, or may be contained in the polymer side chain. Moreover, in the case of a polymer compound, a homopolymer may be sufficient and a copolymer may be sufficient. The compound of the present invention is preferably a low molecular compound.

The T ₁ level (energy level in the lowest triplet excited state) of the host material (A) is preferably 45 Kcal / mol or more (188.3 KJ / mol or more), and 55 Kcal / mol or more (230.1 KJ / mol or more). More preferably, it is 60 Kcal / mol or more (251.1 KJ / mol or more).

Next, general formula (1) will be described. L represents a single bond or a linking group comprising a divalent to octavalent aromatic ring, a divalent to octavalent aromatic heterocyclic ring, a carbon atom, a nitrogen atom or a silicon atom . The linking group represented by L is preferably a linking group formed of C, N, O, S, Si, Ge, etc., more preferably a single bond, a carbon atom, a silicon atom, a germanium atom, an aromatic ring, Heterocycle, more preferably an arylene group, a carbon atom, or a silicon atom.

  Specific examples of the linking group represented by L include the following in addition to a single bond.

  The linking group represented by L is preferably a divalent or higher valent aromatic ring, a divalent or higher aromatic heterocyclic ring, a carbon atom or a silicon atom, more preferably a divalent or higher benzene, divalent or higher naphthalene, 2 Valence or more anthracene, valence 2 or more biphenyl, valence 2 or more terphenyl, valence 2 or more triphenylene, valence 2 or more phenanthrene, valence 2 or more triazole, valence 2 or more pyridine, valence 2 or more pyrimidine, carbon atom And a silicon atom, and more preferably, a divalent or higher benzene, a divalent or higher biphenyl, a divalent or higher triazole, a carbon atom, or a silicon atom.

  The linking group represented by L may have a substituent, and the substituent is as defined above. The substituent is preferably a phenyl group or a biphenyl group.

  T represents a group containing a triphenylene structure and may be different from each other or the same. The triphenylene structure contained in T may have a substituent and may be bonded to each other to form a ring. The substituent has the same meaning as the above substituent.

n represents an integer of 2 to 8, good Mashiku is an integer from 2 to 4.

  Next, although the example of host material (A) used for this invention is shown, this invention is not limited to this.

  Next, a method for producing the compound of the host material (A) used in the present invention will be described. A host material that includes this triphenylene structure but does not exhibit liquid crystallinity can be synthesized by utilizing various aromatic carbon-carbon bond forming reactions, for example, Organic Synthesis Reaction Guide (John Wiley & Sons, Inc.). P. 617-p. 643 and Comprehensive Organic Transformation (VCH) p. 5-p. 103 can be synthesized using the technique described in 103.

Next, in the light emitting layer of the light emitting device of the present invention, a metal complex host material may be used as the host material (B) together with the host material (A). The metal ions in the metal complex constituting the host material (B) are not particularly limited, but are preferably beryllium ions, magnesium ions, aluminum ions, gallium ions, and zinc ions, and more preferably beryllium ions, aluminum ions, and zinc ions. And more preferably zinc ions.
The amount of the host material (B) used relative to the host material (A) is preferably 80% by mass or less, more preferably 20 to 50% by mass.

  The ligand contained in the metal complex as the host material (B) includes various ligands, preferably a nitrogen-containing heterocyclic ligand (preferably having a carbon number of 1 to 30, more preferably a carbon number). 2 to 20, particularly preferably 3 to 15 carbon atoms, which may be a monodentate ligand or a bidentate or higher ligand, preferably a bidentate ligand such as pyridine coordination , Bipyridyl ligand, quinolinol ligand, hydroxyphenylazole ligand (hydroxyphenylbenzimidazole, hydroxyphenylbenzoxazole ligand, hydroxyphenylimidazole ligand)), alkoxy ligand ( Preferably it is C1-C30, More preferably, it is C1-C20, Most preferably, it is C1-C10, for example, methoxy, ethoxy, butoxy, 2 Ethylhexyloxy, etc.), aryloxy ligands (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms such as phenyloxy, 1- Naphthyloxy, 2-naphthyloxy, 2,4,6-trimethylphenyloxy, 4-biphenyloxy, etc.).

Heteroaryloxy ligand (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 pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.) An alkylthio ligand (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), arylthio ligand ( Preferably, it has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenylthio, etc., a heteroarylthio ligand (preferably 1 to 1 carbon atoms). 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as pyridylthio, 2 Benzimidazolylthio, 2-benzoxazolyl thio, and 2-benzthiazolylthio the like.),

Siloxy ligand (preferably having 1 to 30 carbon atoms, more preferably 3 to 25 carbon atoms, particularly preferably 6 to 20 carbon atoms, such as triphenylsiloxy group, triethoxysiloxy group, triisopropylsiloxy group, etc. More preferred are nitrogen-containing heterocyclic ligands, aryloxy ligands, heteroaryloxy groups, and siloxy ligands, and even more preferred are nitrogen-containing heterocyclic ligands and aryloxy ligands. Ligands, siloxy ligands.

  The glass transition point of the metal complex host material (B) contained in the light emitting device of the present invention is preferably 80 ° C. or higher, more preferably 100 ° C. or higher, and further preferably 120 ° C. or higher.

  The metal complex host material (B) of the present invention is preferably a compound represented by the general formula (2) or the general formula (3) or a tautomer thereof (more preferably, represented by the general formula (2)). Or a tautomer thereof), a compound represented by the general formula (4), the general formula (5) or the general formula (6), or a tautomer thereof is more preferable. The compound represented by (4) or a tautomer thereof is more preferable.

The general formula (2) will be described. M ¹¹ represents a metal ion. The metal ions are preferably beryllium ions, magnesium ions, aluminum ions, gallium ions, and zinc ions, more preferably beryllium ions, aluminum ions, and zinc ions, and still more preferably zinc ions.

L ¹¹ represents a ligand. Examples of the ligand include the ligands described for the ligand contained in the metal complex, and the preferred range is also the same.

X ¹¹ is an oxygen atom, a substituted or unsubstituted nitrogen atom, or a sulfur atom, and an oxygen atom is more preferable. Examples of the substituent on the nitrogen atom include —SO ₂ R ^a , —COR ^b or —P (═O) (R ^c ) (R ^d ) (R ^a , R ^b , R ^c , and R ^d represent aliphatic carbonization, respectively. Represents a hydrogen group, an aryl group, a heterocyclic group, an amino group, an alkoxy group, an aryloxy group or a heterocyclic oxy group), and —SO ₂ ^Ra is more preferable.

Q ¹¹ represents an atomic group forming an aromatic ring. Aromatic ring Q ¹¹ is formed, preferably a 4-8 membered ring, more preferably 5- to 6-membered ring. Q ¹¹ and Q ¹² may be bonded to form a condensed ring structure. The aromatic ring formed by Q ¹¹ aromatic hydrocarbon may be either aromatic heterocycle, for example, benzene, thiophene, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyrimidine, pyridazine, thiazole, isothiazole, oxazole, Examples thereof include isoxazole, preferably benzene and pyridine, and more preferably benzene.

The ring formed by Q ¹¹ may have a substituent, and the substituent is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxy group. Carbonyl group, aryloxycarbonyl group, acyloxy group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, halogen atom, cyano group, A heterocyclic group, more preferably an alkyl group, an alkenyl group, an aryl group, a halogen atom, a cyano group and a heterocyclic group, still more preferably an alkyl group, an alkenyl group, an aryl group and a heterocyclic group, particularly preferably Is an alkyl or alkenyl group An aryl group or an aromatic heterocyclic group.

Q ¹² represents an atomic group forming a nitrogen-containing aromatic ring, and the nitrogen-containing aromatic ring formed by Q ¹² is preferably a 4- to 8-membered ring, more preferably a 5- to 6-membered ring. The nitrogen-containing aromatic ring preferably has 2 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 3 to 15 carbon atoms, and particularly preferably 4 to 10 carbon atoms. The nitrogen-containing aromatic ring formed by Q ^12, for example pyridine, quinoline, pyrazine, pyridazine, isoquinoline, quinoxaline, benzoxazole, benzimidazole, benzothiazole, indolenine pyrazole, oxadiazole, pyrazolotriazole, isoxazole, Examples include triazole, thiadiazole, pyrrolotriazole, and imidazotriazole, preferably pyridine, quinoline, pyrazine, benzoxazole, benzimidazole, benzimidazole, oxadiazole, triazole, pyrazolotriazole, pyrrolotriazole, and thiadiazole, and more preferable. Are benzoxazole, benzimidazole and oxadiazole.

Q ¹² may have a substituent, and examples of the substituent include the groups described in Q ¹¹ above.

m ¹¹ represents an integer of 0 to 3, 0, 1 are preferred, more preferably 0. m ¹² represents an integer of 1 to 4, 2, 3 are preferred, 3 is more preferable.

The general formula (3) will be described. L ²¹ and X ²¹ have the same meanings as L ¹¹ and X ¹¹ , and preferred ranges are also the same. , M ²¹ represents an integer of 0 to 3, preferably 0, 1 and more preferably 0. m ²² represents an integer of 1 to 4, preferably 2, 3, and more preferably 3.

M ²¹ represents a metal ion. The metal ions are preferably beryllium ions, magnesium ions, aluminum ions, gallium ions, and zinc ions, more preferably beryllium ions, aluminum ions, and zinc ions, and still more preferably aluminum ions.

Q ²¹ represents an atomic group forming an aromatic ring. The aromatic ring formed by Q ²¹ may be either an aromatic hydrocarbon or an aromatic heterocycle, and the number of members is the same as described for Q ¹¹ , preferably benzene or pyridine, more preferably Benzene.

Q ²² represents an atomic group forming a nitrogen-containing aromatic ring, preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 3 to 15 carbon atoms, and particularly preferably 4 to 10 carbon atoms. is there. Ring number-membered nitrogen-containing aromatic ring formed by Q ²² is the same as described in Q ^12, preferably pyridine, pyrazine, more preferably pyridine.

The general formula (4) will be described. L ³¹ , M ³¹ , m ³¹ and m ³² have the same meanings as L ¹¹ , M ¹¹ , m ¹¹ and m ¹² , and preferred ranges are also the same. R ¹⁰¹ represents a substituent, preferably an alkyl group. m ³³ represents an integer of 0 to 4, and 0 and 1 are preferable.

Y ³¹ represents an oxygen atom, a sulfur atom, a selenium atom or a substituted or unsubstituted nitrogen atom, preferably an oxygen atom or a substituted or unsubstituted nitrogen atom. The substituent on the nitrogen atom is preferably an alkyl group or an aryl group.

Q ³¹ represents an atomic group forming an aromatic ring. The aromatic ring formed by Q ³¹ may be any aromatic hydrocarbon, aromatic heterocyclic, its membered ring is the same as described in Q ^11, preferably benzene, pyridine.

The general formula (5) will be described. L ⁴¹ , M ⁴¹ , R ¹¹¹ , Y ⁴¹ , m ⁴¹ , m ⁴² , and m ⁴³ are synonymous with L ¹¹ , M ¹¹ , R ¹⁰¹ , Y ³¹ , m ¹¹ , m ¹² , and m ³³ , and preferred ranges are also included. The same. R ¹¹² represents a substituent, preferably an alkyl group, an aryl group or a heteroaryl group, more preferably an alkyl group or an aryl group.

The general formula (6) will be described. L ⁵¹ , M ⁵¹ , R ¹²¹ , m ⁵¹ and m ⁵² have the same meanings as L ²¹ , M ²¹ , R ¹⁰¹ , m ²¹ and m ²² , and preferred ranges are also the same. m ⁵³ represents an integer of 0 to 6, and 0 and 1 are preferable.

  Although the compound example of the metal complex host material (B) of this invention is shown, this invention is not limited to this.

  The present invention further includes an organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, and contains at least one material represented by the following general formula (1A) or (1B). The present invention relates to an organic electroluminescent element.

  In this case, the compounds of the general formula (1A) and the general formula (1B) may be contained in any of the organic layers, but are preferably contained as a host material in the hole transport layer or the light emitting layer.

  When the compound represented by the general formula (1A) or the general formula (1B) is included in the light-emitting element of the present invention, the light-emitting material is a fluorescent compound that emits light from singlet excitons or a triplet exciton. Any phosphorescent compound that emits light may be used, but a phosphorescent material is more preferable from the viewpoint of luminous efficiency and durability.

  Examples of luminescent materials include benzoxazole and derivatives thereof, benzimidazole and derivatives thereof, benzothiazole and derivatives thereof, styrylbenzene and derivatives thereof, polyphenyl and derivatives thereof, diphenylbutadiene and derivatives thereof, and tetraphenylbutadiene. And their derivatives, naphthalimide and their derivatives, coumarin and their derivatives, condensed aromatic compounds, perinones and their derivatives, oxadiazole and their derivatives, oxazine and their derivatives, aldazine and their derivatives, pyralidine And their derivatives, cyclopentadiene and their derivatives, bisstyrylanthracene and their derivatives, quinacridone and their derivatives Pyrrolopyridine and derivatives thereof, thiadiazolopyridine and derivatives thereof, cyclopentadiene and derivatives thereof, styrylamine and derivatives thereof, diketopyrrolopyrrole and derivatives thereof, aromatic dimethylidin and compounds thereof, 8-quinolinol Metal complexes of these and their derivatives, pyromethene and metal complexes of these derivatives, various metal complexes represented by rare earth complexes, transition metal complexes, etc., polymer compounds such as polythiophene, polyphenylene, polyphenylene vinylene, organic silanes and their derivatives, etc. Is mentioned. The light-emitting material is preferably a condensed aromatic compound, quinacridone and derivatives thereof, diketopyrrolopyrrole and derivatives thereof, metal complexes of pyromethene and derivatives thereof, rare earth complexes, transition metal complexes, more preferably condensed aromatic compounds , A transition metal complex.

Next, general formula (1A) will be described.

In the formula, each T ¹ represents a group containing a triphenylene structure which may be the same or different. The group containing a triphenylene structure represented by T ¹ is synonymous with the group containing a triphenylene structure described for T, and the preferred range is also the same.

Ar ¹ represents an alkyl group, an aryl group, or a heteroaryl group, which may be the same or different. Ar ¹ is preferably a methyl group, an ethyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, or a pyridyl group, more preferably a methyl group, a phenyl group, or an anthryl group, and most preferably a phenyl group.

Ar ¹ may have a substituent, and examples of the substituent are the same as those of the substituent. The substituent that Ar ¹ may have is preferably a phenyl group or a biphenyl group, and most preferably a phenyl group.

  p represents an integer of 2 to 4, and p is preferably 2 or 3, and 2 is most preferable.

一般式（１）は好ましくは一般式（１Ｂ）である。式中、T²はそれぞれ同じでも異なっていても良いトリフェニレン構造を含む基を表す。T²で表されるトリフェニレン構造を含む基は前記Tで説明したトリフェニレン構造を含む基と同義であり、好ましい範囲も同じである。 Next, general formula (1B) will be described.

The general formula (1) is preferably the general formula (1B). In the formula, each T ² represents a group containing a triphenylene structure which may be the same or different. The group containing a triphenylene structure represented by T ² is synonymous with the group containing a triphenylene structure described for T, and the preferred range is also the same.

Ar ² represents an alkyl group, an aryl group or a heteroaryl group which may be the same or different. Ar ² is preferably a methyl group, an ethyl group, a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, or a pyridyl group, more preferably a methyl group, a phenyl group, or an anthryl group, and most preferably a phenyl group.

Ar ² may have a substituent, and examples of the substituent are the same as those of the substituent. The substituent that Ar ² may have is preferably a phenyl group or a biphenyl group, and most preferably a phenyl group.

L ² represents a divalent to hexavalent linking group. Divalent or hexavalent following linking group A arylene group represented by L ^2, a heteroarylene group.

The arylene group represented by L ² is an arylene group of a condensed ring in which a single ring or two or more rings are condensed, preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably. C6-C12, for example, phenylene group, biphenylene group, terphenylene group, naphthylene group, anthrylene group, phenanthrenylene group, pyrenylene group, peryleneylene group, fluorenylene group, rubrenylene group, chrysenylene group, triphenylenylene group Benzoanthrylene group, benzophenanthrylene group, diphenylanthrylene group and the like.

The heteroarylene group represented by L ² is a condensed heteroaryl group in which a single ring or two or more rings are condensed, preferably 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and still more preferably 2 to 2 carbon atoms. 10 heteroaryl groups such as pyridylene group, quinolylene group, isoquinolylene group, acridinylene group, phenanthridinylene group, pyrazinylene group, quinoxalinylene group, pyrimidinylene group, triadylene group, imidazolylene group, pyrazolylene group, oxadiazolylene group, Examples thereof include a triazorylene group, a furylene group, a thienylene group, a pyrrolylene group, an indylene group, and a carbazolylene group.

L ² may be a group in which the arylene group and the heteroarylene group are connected to each other.

The arylene group and heteroarylene group represented by L ² are preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthrylene group, a pyridylene group, a pyrimidylene group, a triadylene group, an oxadiazolylene group, a triazolylene group, and a thienylene group. , A pyrrolylene group, an indolylene group, and a carbazolylene group, more preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a pyridylene group, a triadylene group, an oxadiazolylene group, a thienylene group, and a carbazolylene group, and more preferably A phenylene group, a biphenylene group, and a pyridylene group, and most preferably a metaphenylene group.

q represents an integer of 2 to 6 . good Mashiku as the q is 2 to 4 integer, most preferably 2 or 3.

  As specific examples of the general formula (1A), among the compound examples represented as specific examples of the host material (A), for example, compounds (1-4), (1-15), (1-20), (1- 21), (1-22), (1-23), and compounds represented by (1-24) are exemplified, but the present invention is not limited thereto.

  Specific examples of the general formula (1B) include, for example, the compounds (1-14), (1-16), (1-17), (1- 18) and compounds represented by (1-19) are exemplified, but the present invention is not limited thereto.

Next, the manufacturing method of the compound represented by general formula (1A) and general formula (1B) is demonstrated.
The compound represented by the general formula (1A) can be synthesized from a halogen-substituted product of a triphenylene derivative using various carbon-silicon bond forming reactions, and the method thereof is not particularly limited. For example, the chemistry of -It can synthesize | combine using the method described in Organic Silicon compounds (The Chemistry of Organic Silicon compounds), part 1, John Wiley & Sons, P.655-761.
This method is, for example, a method in which an organometallic compound of a triphenylene derivative is synthesized from a halogen-substituted product of a triphenylene derivative by a halogen-metal exchange reaction, and this is reacted with a halosilane compound.

The compound represented by the general formula (1B) can be synthesized from a halogen-substituted product of a triphenylene derivative by using various carbon-nitrogen bond forming reactions, and the method is not particularly limited. For example, Journal of American・ Chemical Society (Journal of American Chemical Society), 1996, 118, 7215, or Journal of American Chemical Society, 1996, 118, 7217, etc. A method of synthesis using a method using a palladium catalyst is preferred.
This method is, for example, a method of catalytically coupling a halogen-substituted product of a triphenylene derivative and an arylamine compound in the presence of a palladium catalyst and a base.

The palladium catalyst is not particularly limited, and examples thereof include palladium tetrakistriphenylphosphine, palladium carbon, palladium acetate, palladium dichloride (dppf) (dppf: 1,1′-bisdiphenylphosphinoferrocene) and the like. A ligand such as triphenylphosphine or P (t-Bu) ₃ may be added simultaneously.

  In the synthetic carbon-nitrogen bond forming reaction of the general formula (1B), it is preferable to use a base. Although the kind of base to be used is not particularly limited, examples thereof include sodium carbonate, sodium acetate, potassium carbonate, rubidium carbonate, triethylamine, sodium t-butoxy, potassium t-butoxy and the like. The amount of the base to be used is not particularly limited, but is preferably 0.1 to 20 equivalents, particularly preferably 1 to 10 equivalents with respect to carbazole or a derivative thereof, iminostilbene or a derivative thereof.

  The carbon-nitrogen bond forming reaction in the synthesis of the general formula (1B) is preferably performed using a solvent. Although the solvent to be used is not particularly limited, for example, ethanol, water, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethylformamide, toluene, tetrahydrofuran, xylene, mesitylene, and a mixed solvent thereof can be used.

  The reaction temperature of the carbon-nitrogen bond forming reaction when synthesizing the compound of the general formula (1B) is not particularly limited, but is preferably 20 to 220 ° C, preferably 20 to 180 ° C, more preferably 20 to 160. ° C.

  Next, the light emitting device of the present invention will be described. The light emitting device of the present invention is not particularly limited as long as it is a device using the compound of the present invention, and the system, driving method, usage form and the like are not particularly limited. An organic EL (electroluminescence) element can be mentioned as a typical light emitting element.

  The method for forming the organic layer of the light-emitting device containing the compound of the present invention is not particularly limited, but methods such as resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method, inkjet method, printing method, etc. In view of characteristics and production, resistance heating vapor deposition, coating method, and transfer method are preferable.

  The light-emitting device of the present invention is a device in which a light-emitting layer or a plurality of organic compound films including a light-emitting layer is formed between a pair of anode and cathode electrodes. In addition to the light-emitting layer, a hole injection layer, a hole transport layer, and an electron injection It may have a layer, an electron transport layer, a protective layer, etc., and each of these layers may have other functions. Various materials can be used for forming each layer.

  The anode supplies holes to a hole injection layer, a hole transport layer, a light emitting layer, and the like, and a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Is a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide and indium tin oxide (ITO), metals such as gold, silver, chromium and nickel, and these metals and conductive metal oxides. Inorganic conductive materials such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, preferably conductive metals It is an oxide, and ITO is particularly preferable from the viewpoint of productivity, high conductivity, transparency, and the like. Although the film thickness of the anode can be appropriately selected depending on the material, it is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 500 nm.

As the anode, a layer formed on a soda-lime glass, non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass 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. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength, but when glass is used, a thickness of 0.2 mm or more, preferably 0.7 mm or more is usually used.
Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating vapor deposition method, a chemical reaction method (sol-gel method, etc.), a coating of a dispersion of indium tin oxide, etc. A film is formed by this method.
The anode can be subjected to cleaning or other treatments to lower the drive voltage of the element or increase the light emission efficiency. For example, in the case of ITO, UV-ozone treatment, plasma treatment, etc. are effective.

  The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, etc., and the adhesion, ionization potential, stability, etc., between the negative electrode and the adjacent layer such as the electron injection layer, electron transport layer, light emitting layer, etc. Selected in consideration of As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples include an alkali metal (for example, Li, Na, K, etc.) and its fluoride. Or oxides, alkaline earth metals (eg Mg, Ca, etc.) and fluorides or oxides thereof, gold, silver, lead, aluminum, sodium-potassium alloys or their mixed metals, lithium-aluminum alloys or their mixtures Examples thereof include metals, magnesium-silver alloys or mixed metals thereof, rare earth metals such as indium and ytterbium, preferably materials having a work function of 4 eV or less, more preferably aluminum, lithium-aluminum alloys or mixed metals thereof. , Magnesium-silver alloys or mixed metals thereof. The cathode can take not only a single layer structure of the compound and the mixture but also a laminated structure including the compound and the mixture. For example, a laminated structure of aluminum / lithium fluoride and aluminum / lithium oxide is preferable. The film thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, still more preferably 100 nm to 1 μm.

For production of the cathode, methods such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, and a coating method are used, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, a plurality of metals can be vapor-deposited simultaneously to form an alloy electrode, or a previously prepared alloy may be vapor-deposited.
The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

  The material of the light emitting layer is a function that can inject holes from the anode or hole injection layer, hole transport layer and cathode or electron injection layer, electron transport layer when an electric field is applied, Any material can be used as long as it can form a layer having a function of transferring injected charges and a function of emitting light by providing a recombination field of holes and electrons, such as benzoxazole, benzimidazole, and benzothiazole. , Styrylbenzene, polyphenyl, diphenylbutadiene, tetraphenylbutadiene, naphthalimide, coumarin, perylene, perinone, oxadiazole, aldazine, pyralidine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, cyclopentadiene , Styrylamine, Aromatic dimethylidene compound, various metal complexes represented by metal complexes or rare earth complexes of 8-quinolinol,

Examples thereof include polymer compounds such as polythiophene, polyphenylene, and polyphenylene vinylene, organic silanes, iridium trisphenylpyridine complexes, transition metal complexes typified by platinum porphyrin complexes, and derivatives thereof. At least one of the materials of the light emitting layer is a phosphorescent material. Although the film thickness of a light emitting layer is not specifically limited, Usually, the thing of the range of 1 nm-5 micrometers is preferable, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm.
The method for forming the light emitting layer is not particularly limited, but resistance heating vapor deposition, electron beam, sputtering, molecular lamination method, coating method (spin coating method, casting method, dip coating method, etc.), inkjet method, printing method , LB method, transfer method and the like are used, preferably resistance heating vapor deposition and coating method.

  The light emitting layer may be formed of a single compound or a plurality of compounds. Further, the light emitting layer may be one or plural, and each layer may emit light with different emission colors, for example, white light may be emitted. White light may be emitted from a single light emitting layer. When there are a plurality of light emitting layers, each light emitting layer may be formed of a single material or may be formed of a plurality of compounds.

The material of the hole injection layer and the hole transport layer may be any one having a function of injecting holes from the anode, a function of transporting holes, or a function of blocking electrons injected from the cathode. Good. Specific examples thereof include carbazole, triazole, oxazole, oxadiazole, imidazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone, hydrazone, stilbene, silazane, aromatic first Tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds, poly (N-vinylcarbazole), aniline copolymers, thiophene oligomers, conductive polymer oligomers such as polythiophene, organic Examples thereof include silane derivatives, carbon films, compounds of the present invention, and derivatives thereof. The film thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 nm. . The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the materials described above, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.
As a method for forming the hole injection layer and the hole transport layer, a vacuum deposition method, an LB method, a method in which the hole injection / transport material is dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating method). Etc.), an inkjet method, a printing method, and a transfer method are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, and the like.

The material for the electron injection layer and the electron transport layer may be any material having any one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Specific examples include fragrances such as triazole, oxazole, oxadiazole, imidazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyrandioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, naphthalene, and perylene. Ring tetracarboxylic anhydride, phthalocyanine, metal complexes of 8-quinolinol, metal phthalocyanine, various metal complexes represented by metal complexes having benzoxazole or benzothiazole as a ligand, organic silane, compound of the present invention, and Examples thereof include derivatives thereof. Although the film thickness of an electron injection layer and an electron carrying layer is not specifically limited, The thing of the range of 1 nm-5 micrometers is preferable normally, More preferably, it is 5 nm-1 micrometer, More preferably, it is 10 nm-500 nm. The electron injection layer and the electron 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.
As a method for forming the electron injection layer and the electron transport layer, a vacuum deposition method, an LB method, a method in which the electron injection / transport material is dissolved or dispersed in a solvent (a spin coating method, a casting method, a dip coating method, etc.), An ink jet method, a printing method, a transfer method, or the like is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

As a material for the protective layer, any material may be used as long as it has a function of preventing substances 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 fluorides such as MgF ₂ , LiF, AlF ₃ , and CaF ₂ , SiN _x , SiO _x N _y Such as nitride, polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, tetrafluoroethylene And a copolymer obtained by copolymerizing a monomer mixture containing at least one comonomer, a fluorine-containing copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0 .1% or less of moisture-proof substances and the like.
There is no particular limitation on the method for forming the protective layer. For example, vacuum deposition, sputtering, reactive sputtering, MBE (molecular beam epitaxy), cluster ion beam, ion plating, plasma polymerization (high frequency excitation ions) Plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method, printing method, and transfer method can be applied.

[合成例２] 例示化合物（１−１５）の合成
窒素気流下、合成例１で合成した２−ブロモトリフェニレンA ０．５５ｇ、エーテル４０ｍｌを氷冷し、ここに1.6mol/lのノルマルブチルリチウム/ヘキサン溶液１．２ｍｌを１０分かけて滴下した。滴下終了後、氷浴をはずして室温まで昇温し、さらに攪拌した。３０分後再び氷冷して、ここにジクロロジフェニルシラン０．２ｇを１０分かけて滴下し、滴下終了後、室温まで昇温してさらに攪拌を続けた。3時間後、1.0mol/lの塩酸水溶液２０ｍｌを滴下し、滴下終了後、さらにクロロホルム５０ｍｌ、水５０ｍｌを加えた。分液して得られた有機層を水洗後、硫酸マグネシウムで乾燥、ろ過後、溶媒を減圧下留去した。得られた固体をカラムクロマトグラフィー（ヘキサン/クロロホルム）で精製し、ヘキサン/クロロホルム混合溶媒から再結晶することで例示化合物（１−１５）０．７２ｇを得た。本化合物の融点は２４４℃であった。

[合成例３] 化合物Bの合成
ｍ−フェニレンジアミン１８．５ｇ、ピリジン１７ｍｌ中に氷冷下、無水酢酸３２．５ｇを２０分かけて滴下し、室温に昇温して攪拌を続けた。８時間後、これにベンゼン１２０ｍｌを加え、析出した固体をろ取することで化合物B ３０．１ｇを得た。
[合成例４] 化合物Cの合成
窒素気流下、合成例３で合成した化合物B １０．０ｇ、ヨードベンゼン２７．６ｇ、炭酸カリウム２３.０ｇ、銅粉０．７ｇ、ヨウ素０．０３ｇを１８０℃に加熱し、１０時間攪拌した。反応の進行をTLC（薄層クロマトグラフィー）で追跡し、化合物Bの消失を確認した後、反応混合物中にクロロホルム１００ｍｌ、水１００ｍｌを加え、分液した。得られた有機層を硫酸マグネシウムで乾燥させ、硫酸マグネシウムをろ過後、溶媒を減圧留去した。得られた固体をメタノールから再結晶することで化合物C ５．３ｇを得た。
[合成例５] 化合物Dの合成
合成例４で合成した化合物C ５．０ｇ、エタノール１００ｍｌ中に水酸化カリウム６．０ｇを加え、加熱還流した。８時間後室温まで冷却し、ここに水４０ｍｌを加え、析出した固体をろ取した。得られた固体をメタノールで再結晶することで化合物D ３．５ｇを得た。

[合成例６] 例示化合物（１−１６）の合成
窒素気流下、合成例１で合成した２−ブロモトリフェニレンA １．０ｇ、合成例５で合成した化合物D ０．４ｇ、２酢酸パラジウム ３５ｍｇ、トリス-ｔ−ブチルホスフィン０．１０ｇ、ｔ-ブトキシナトリウム０．６０ｇ、メシチレン３０ｍｌを加熱還流し、８時間攪拌した。反応の進行をTLC（薄層クロマトグラフィー）で追跡し、２−ブロモトリフェニレンAの消失を確認した後、反応混合物中にクロロホルム５０ｍｌ、水５０ｍｌを加え、分液した。得られた有機層を硫酸マグネシウムで乾燥させ、ろ過後、溶媒を減圧留去した。得られた固体をカラムクロマトグラフィー（ヘキサン/クロロホルム）で精製した後、ヘキサン/クロロホルム混合溶媒から再結晶することで例示化合物（１−１６） ０．６０ｇを得た。本化合物の融点は２５８℃であった。

［実施例１］
洗浄したＩＴＯ基板を蒸着装置に入れ、まず正孔輸送材料としてα−ＮＰＤ（Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ジ（α−ナフチル）−ベンジジン）を５０ｎｍ蒸着した。この上に化合物（１−１）と 化合物a を １７対１ の比率（重量比）で３６ｎｍの厚さに共蒸着し、この上にアゾ−ル化合物ｂを３６ｎｍ蒸着した。有機薄膜上にパターニングしたマスク（発光面積が４ｍｍ×５ｍｍとなるマスク）を設置し、蒸着装置内でフッ化リチウムを約１ｎｍ蒸着し、この上にアルミニウムを膜厚約２００ｎｍ蒸着して素子を作製した。東陽テクニカ製ソースメジャーユニット２４００型を用いて、直流定電圧をＥＬ素子に印加し発光させ、その輝度をトプコン社の輝度計ＢＭ−８、発光波長を浜松フォトニクス社製スペクトルアナライザーＰＭＡ−１１を用いて測定した。
その結果、色度値（０．２７、０．６２）の緑色発光が得られ、素子の外部量子効率は ７．１％ であった。
また本素子の素子耐久性評価を初期輝度１２００ｃｄ/m²、電流値一定にて行うと半減時間４００時間である。 Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited thereto.
[Synthesis Example 1] Synthesis of 2-bromotriphenylene A 2.3 g of bromine was dropped into 100 ml of triphenylene, 0.15 g of iron powder and 100 ml of carbon disulfide over 10 minutes. After completion of the dropwise addition, stirring was continued and the mixture was stirred overnight, followed by liquid separation by adding 50 ml of water and 50 ml of chloroform. The obtained organic layer was washed with water and dried over magnesium sulfate. After filtration through magnesium sulfate, the solvent was distilled off under reduced pressure, and the resulting solid was purified by column chromatography (hexane / chloroform) to obtain 3.0 g of 2-bromotriphenylene A.

[Synthesis Example 2] Synthesis of Exemplified Compound (1-15) Under a nitrogen stream, 0.55 g of 2-bromotriphenylene A synthesized in Synthesis Example 1 and 40 ml of ether were ice-cooled, and 1.6 mol / l normal butyl lithium was added thereto. 1.2 ml of hexane solution was added dropwise over 10 minutes. After completion of the dropwise addition, the ice bath was removed, the temperature was raised to room temperature, and the mixture was further stirred. After 30 minutes, the mixture was ice-cooled again, and 0.2 g of dichlorodiphenylsilane was added dropwise over 10 minutes. After completion of the addition, the mixture was warmed to room temperature and further stirred. Three hours later, 20 ml of a 1.0 mol / l hydrochloric acid aqueous solution was added dropwise, and after completion of the dropwise addition, 50 ml of chloroform and 50 ml of water were further added. The organic layer obtained by liquid separation was washed with water, dried over magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained solid was purified by column chromatography (hexane / chloroform), and recrystallized from a mixed solvent of hexane / chloroform to obtain 0.72 g of exemplary compound (1-15). The melting point of this compound was 244 ° C.

[Synthesis Example 3] Synthesis of Compound B 32.5 g of acetic anhydride was added dropwise to 18.5 g of m-phenylenediamine and 17 ml of pyridine under ice-cooling over 20 minutes, and the temperature was raised to room temperature and stirring was continued. After 8 hours, 120 ml of benzene was added thereto, and the precipitated solid was collected by filtration to obtain 30.1 g of Compound B.
[Synthesis Example 4] Synthesis of Compound C In a nitrogen stream, 10.0 g of Compound B synthesized in Synthesis Example 3, 27.6 g of iodobenzene, 23.0 g of potassium carbonate, 0.7 g of copper powder, and 0.03 g of iodine were added at 180 ° C. And stirred for 10 hours. The progress of the reaction was monitored by TLC (thin layer chromatography), and disappearance of Compound B was confirmed. Then, 100 ml of chloroform and 100 ml of water were added to the reaction mixture, and the mixture was separated. The obtained organic layer was dried over magnesium sulfate, and after filtering the magnesium sulfate, the solvent was distilled off under reduced pressure. The obtained solid was recrystallized from methanol to obtain 5.3 g of Compound C.
[Synthesis Example 5] Synthesis of Compound D To 5.0 g of Compound C synthesized in Synthesis Example 4 and 6.0 g of potassium hydroxide in 100 ml of ethanol, the mixture was heated to reflux. After 8 hours, the mixture was cooled to room temperature, 40 ml of water was added thereto, and the precipitated solid was collected by filtration. The obtained solid was recrystallized from methanol to obtain 3.5 g of Compound D.

[Synthesis Example 6] Synthesis of Exemplified Compound (1-16) Under a nitrogen stream, 1.0 g of 2-bromotriphenylene A synthesized in Synthesis Example 1, 0.4 g of Compound D synthesized in Synthesis Example 5, 35 mg of palladium acetate, 0.10 g of tris-t-butylphosphine, 0.60 g of sodium t-butoxy, and 30 ml of mesitylene were heated to reflux and stirred for 8 hours. The progress of the reaction was followed by TLC (thin layer chromatography), and after confirming the disappearance of 2-bromotriphenylene A, 50 ml of chloroform and 50 ml of water were added to the reaction mixture, followed by liquid separation. The obtained organic layer was dried over magnesium sulfate and filtered, and then the solvent was distilled off under reduced pressure. The obtained solid was purified by column chromatography (hexane / chloroform) and then recrystallized from a mixed solvent of hexane / chloroform to obtain 0.60 g of exemplary compound (1-16). The melting point of this compound was 258 ° C.

[Example 1]
The cleaned ITO substrate was put into a vapor deposition apparatus, and α-NPD (N, N′-diphenyl-N, N′-di (α-naphthyl) -benzidine) was first vapor-deposited as a hole transport material by 50 nm. On top of this, compound (1-1) and compound a were co-deposited in a ratio of 17: 1 (weight ratio) to a thickness of 36 nm, and on this, an azole compound b was vapor-deposited 36 nm. A patterned mask (a mask with a light emission area of 4 mm x 5 mm) is placed on the organic thin film, lithium fluoride is deposited in a vapor deposition device at about 1 nm, and aluminum is deposited on the film to a thickness of about 200 nm to produce a device. did. Using a source measure unit model 2400 made by Toyo Technica, applying a DC constant voltage to the EL element to emit light, using a luminance meter BM-8 from Topcon and a spectrum analyzer PMA-11 from Hamamatsu Photonics. Measured.
As a result, green light emission with a chromaticity value (0.27, 0.62) was obtained, and the external quantum efficiency of the device was 7.1%.
When the element durability of this element is evaluated at an initial luminance of 1200 cd / m ² and a constant current value, the half time is 400 hours.

[Example 2]
A device in which the compound (1-1) and the metal complex (2-9) were mixed at a weight ratio of 1: 1 instead of the compound (1-1) was evaluated in the same manner as in Example 1. As a result, green light emission with a chromaticity value (0.28, 0.62) was obtained, and the external quantum efficiency of the device was 12.1%.
When the element durability of this element is evaluated at an initial luminance of 1200 cd / m ² and a constant current value, the half time is 820 hours.

[Example 3]
A device (1-16) was used in place of NPD, and a device (d) was used in place of compound (1-1), and device preparation was evaluated in the same manner as in Example 1. As a result, green light emission with a chromaticity value (0.28, 0.62) was obtained, and the external quantum efficiency of the device was 10.0%.

[Example 4]
A device (1-2) was used instead of the compound (1-1), and the device was evaluated in the same manner as in Example 1. As a result, green light emission with a chromaticity value (0.27, 0.60) was obtained, and the external quantum efficiency of the device was 8.1%.
When the element durability of this element is evaluated at an initial luminance of 1200 cd / m ² and a constant current value, the half time is 530 hours.

[Example 5]
Using the compound (1-15) instead of the compound (1-1), a device was prepared and evaluated in the same manner as in Example 1. As a result, green light emission with a chromaticity value (0.27, 0.64) was obtained, and the external quantum efficiency of the device was 9.0%.

[Comparative Example 1]
The device was evaluated in the same manner as in Example 1 except that CBP (4,4′-bis (N-carbazolyl) biphenyl) was used instead of the compound (1-1).
When the element durability of this element is evaluated at an initial luminance of 1200 cd / m ² and a constant current value, the half time is 70 hours.

[Comparative Example 2]
The device c was prepared and evaluated in the same manner as in Example 1 using Compound c instead of Compound (1-1). As a result, green light emission with a chromaticity value (0.26, 0.62) was obtained, and the external quantum efficiency of the device was 2.7%.
When the element durability of this element is evaluated at an initial luminance of 1200 cd / m ² and a constant current value, the half time is 30 hours.

[Comparative Example 3]
The device prepared by the method of Comparative Example 2 was evaluated in the same manner as Comparative Example 2 by raising the temperature to 70 ° C. at which the compound c became the liquid crystal phase temperature. As a result, green light emission with chromaticity values (0.26, 0.64) was obtained, and the external quantum efficiency of the device was 8.1%.
Further, when the element durability of this element is evaluated at an initial luminance of 1200 cd / m ² and a constant current value, the luminance half-life is 80 hours.

  Similarly, a high-efficiency light-emitting element can be produced using other compounds of the present invention.

Claims (5)

An organic electroluminescent device having at least one organic layer including a light emitting layer between a pair of electrodes, and comprising at least a host material (A) for a phosphorescent material comprising a compound represented by the following general formula (1) and one, at least one and wherein the organic electroluminescent device characterized by utilizing phosphorescence from a triplet excited state of the luminescent material of phosphorescent material.
General formula (1) LT _n
(In the formula, L represents a single bond or a linking group composed of a divalent to octavalent aromatic ring, a divalent to octavalent aromatic heterocyclic ring, a carbon atom, a nitrogen atom or a silicon atom , and T has a substituent. and a group having even better triphenylene .n represents an integer of 2 to 8, T is also be independently different from each other, may be the same.) The organic electroluminescence characterized by further containing the compound represented by the following general formula (2) or general formula (3) as a metal complex host material (B) in the light emitting layer of the light emitting element of Claim 1. element.

(In the formula, M ¹¹ and M ²¹ each independently represent a metal ion, and L ¹¹ and L ²¹ each independently represent a ligand. X ¹¹ and X ²¹ are each independently an oxygen atom, substituted or unsubstituted. nitrogen atom, a sulfur ^atom, a ^{Q 11, Q 21 .Q 12,} Q 22 is an atomic group forming a nitrogen-containing aromatic ring each independently representing an atomic group forming an aromatic ring each independently ^{.m 11} And m ²¹ each independently represents an integer of 0 to 3, and m ¹² and m ²² each independently represents an integer of 1 to 4.) The organic electroluminescent element according to claim 1, wherein the linking group L of the general formula (1) is a single bond or any one of the following groups .

The organic electroluminescent element according to claim 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1A).

(Wherein, T ¹ may be the same or different each represent a group containing a good Torifenire emissions may have a substituent, Ar ¹ is an alkyl group which may be the same or different and each an aryl group, Represents a heteroaryl group, p represents an integer of 2 or more and 4 or less. The organic electroluminescent element according to claim 1 or 2, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (1B).

(Wherein, T ² may be the same or different each substituent represents a group containing a good Torifenire emissions have a, Ar ² is an alkyl group which may be the same as or different respectively, aryl groups, Represents a heteroaryl group, L ² represents an arylene group or a heteroarylene group, which is a divalent to hexavalent linking group, and q represents an integer of 2 to 6 .