JP4860504B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescent element (hereinafter referred to as an organic EL element).

  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.

In recent organic EL element development, various researches on reduction of driving voltage, improvement of durability, and improvement of external quantum efficiency have been conducted.
It has been reported that copper phthalocyanine or an amine compound is used as a hole injection material as a technique that enables light emission at a low voltage. However, a device using a known hole injecting material has problems such as a decrease in luminance and a dark spot (non-light emitting portion) when light is emitted for a long time or stored at a high temperature for a long time.

Regarding external quantum efficiency, phosphorescent materials such as trisphenylpyridine iridium complex (see, for example, Patent Document 1) and platinum complexes such as octaethylporphyrin platinum complex (see, for example, Patent Documents 2 and 3). An element containing bismuth has shown high efficiency and has attracted attention.
However, devices containing these phosphorescent materials are not satisfactory in terms of durability, and further improvements have been demanded.

On the other hand, panel mass production methods include vacuum deposition methods using low molecular materials, ink jet methods using high molecular materials, printing methods, etc., but wet coating methods have been studied as methods for easily increasing the area. Yes.
However, since many of the above metal complexes have strong intermolecular interactions and form aggregates, the solubility in a solvent is extremely low, and it is difficult to prepare a wet coating solution that is uniformly dissolved. Furthermore, since the solubility is low, it is difficult to fill the film with a high concentration, which is disadvantageous in terms of durability of the device.
Further, even in the organic EL element, these metal complexes form aggregates and emit light having different wavelengths attributed to the aggregates, so that it is difficult to obtain light with high chromaticity due to turbid emission color.
On the other hand, a device by wet coating using a polymer to which a metal complex such as an iridium complex is bonded is disclosed (for example, see Patent Document 4). However, the light emitting efficiency is low and driving durability is improved. There is a problem to be solved and further improvement is desired.
International Publication No. 00/070655 US Pat. No. 6,303,238 B1 US Pat. No. 6,653,564B1 JP 2003-77675 A

  An object of the present invention is to provide an organic electroluminescent device exhibiting high luminous efficiency and excellent durability. Furthermore, it is providing the organic electroluminescent element suitable for a wet application system.

The present invention has been made in view of the above problems, and is achieved by the following means.
<1> An organic electroluminescence device having at least one organic layer between a pair of electrodes , the compounds represented by the following general formulas (IA), (II-A) and (III-A); And containing at least one of interlock-type compounds selected from the following compounds 1, 3, 5, 7, 9, 11, 13-16, 29, 31, 33, and 35-37. Organic electroluminescent device.
<2> The organic electroluminescent element as described in <1>, wherein the layer containing the interlock compound is a layer formed by a wet coating method.
<3> The organic electroluminescence device according to <2>, wherein the concentration of the interlock type compound when applied by the wet coating method is 0.01% by mass or more and 50% by mass or less.
< 4 > The organic electroluminescent element according to any one of <1> to < 3 > , wherein the layer containing the interlock compound is a hole injection layer.
< 5 > The organic electroluminescent element according to any one of <1> to < 4 >, wherein the layer containing the interlock type compound is a light emitting layer.
<6> The organic electroluminescent element according to <4> or <5>, wherein the hole injection layer has a thickness of 5 nm to 500 nm.
<7> The organic electroluminescent element according to <5> or <6>, wherein the light emitting layer has a thickness of 20 m to 80 nm.

  An object of the present invention is to provide an organic electroluminescent device that exhibits high luminous efficiency and excellent durability. Furthermore, an organic electroluminescent element suitable for the wet coating method is provided.

Hereinafter, the organic electroluminescent element of the present invention (hereinafter sometimes referred to as “organic EL element” as appropriate) will be described in detail.
The light-emitting element of the present invention has a cathode and an anode on a substrate, and an organic compound layer including an organic light-emitting layer (hereinafter sometimes simply referred to as “light-emitting layer”) between both electrodes. In view of the properties of the light emitting element, at least one of the anode and the cathode is preferably transparent.
The organic compound layer in the present invention may be either a single layer or a laminate. As an aspect in the case of lamination, an aspect in which a hole transport layer, a light emitting layer, and an electron transport layer are sequentially laminated 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.

1. Interlock type compound description
In the present invention, the interlock type compounds are compounds represented by the following general formulas (IA), (II-A) and (III-A), and compounds 1, 3, 5, 7, 9 described later. , 11, 13-16, 29, 31, 33, and at least one selected from 35-37.
Next, the interlock type compound used in the organic electroluminescence device of the present invention will be described in detail.
The interlock type compound used in the present invention is a compound in which molecular rings are connected like a chain, and includes a catenane compound. For information on Catenanes compound, "Quarterly chemical review (No.31) Chemical aims to supramolecular" edited by the Chemical Society of Japan (206 pp ～216), to "functional supramolecular" CMC Publishing (38 pp -59) Are listed.
The interlock type compound used in the present invention may have one or a plurality of interlock portions (the structure of the ring of molecules connected in the molecule). A typical structure is a structure represented by the following type I, but a structure in which a ring is connected to a three-dimensional skeleton (for example, a structure represented by type II or type III) may be used.

The interlock type compound may be an organic molecule or a non-metallic complex (for example, a boron complex) or a metal complex. In the case of a metal complex, the metal is not particularly limited, but alkali metals, alkaline earth metals, Al, Ga, transition metals, and rare earth metals are preferable. Specific examples of the metal include, for example, Li, Na, Be, Mg, Ba, Al, Ca, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, Eu, Tb, Yb, etc. are mentioned. In the case of a complex, it may be a mononuclear complex or a binuclear complex. In the case of a binuclear complex, the plurality of metals may be the same or different from each other.
In addition, the interlock type compound used in the present invention is a low molecular weight (preferably having a molecular weight of 350 to 3000, more preferably 400 to 2500, and still more preferably 450 to 2000). The molecular weight may be preferably 3000 or more and 1000000 or less, more preferably 4000 or more and 500000 or less, and still more preferably 5000 or more and 100000 or less.

  The interlock compound used in the present invention is preferably a compound represented by the following general formula (I), (II) or (III).

In general formula (I), M ¹ represents a metal. L ¹¹ , L ¹² , L ¹³ and L ¹⁴ each represent an atomic group coordinated to a metal. Y ¹¹ and Y ¹² each represent a linking group.

In the general formula (II), ^{M 2} represents a metal. L ²¹ , L ²² , L ²³ and L ²⁴ each represent an atomic group coordinated to a metal. Y ²¹ and Y ²² each represent a linking group.

In the general formula (III), ^{M 3} represents a metal. L ³¹ , L ³² , L ³³ , L ³⁴ , L ³⁵ and L ³⁶ each represent an atomic group coordinated to a metal. Y ³¹ and Y ³² each represent a linking group.

The compound represented by formula (I) will be described in detail.
The metal represented by M ¹ is not particularly limited, but is preferably 0 to 4 valence, more preferably 1 to 3 valence. Specific examples of the metal represented by M ¹ include, for example, Be, Mg, Ba, Al, Ca, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, Au, Eu, Tb, Yb, etc. are mentioned. Preferably, as the metal, when the compound represented by the general formula (I) is used as a hole transport material (hole injection material, hole transport material, electron blocking material, light emitting layer host material, etc.), Cu, Ru, Rh, Pd and Ir, more preferably Cu and Ir, and particularly preferably Cu.
When the compound represented by the general formula (I) is used as an electron transport material (electron injection material, electron transport material, hole blocking material, light emitting layer host material, etc.), Be, Mg, Al, Zn, Ga, Ru , Rh, Pd, and Pt are preferable, Be, Al, Zn, Pd, and Pt are more preferable, and Be, Zn, Pd, and Pt are particularly preferable. When the compound represented by the general formula (I) is used as a light emitting material, Cu, Ru, Rh, Pd, Re, Ir, and Pt are preferable, and Ru, Rh, Pd, Re, and Pt are more preferable. , Pt is particularly preferred.

The atomic group that coordinates to M ¹ represented by L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ (the bond formed by coordination includes, for example, a coordinate bond, a covalent bond, and an ionic bond) Although not limited, for example, an atomic group coordinated by a carbon atom, an atomic group coordinated by a nitrogen atom, an atomic group coordinated by an oxygen atom, an atomic group coordinated by a sulfur atom, an atomic group coordinated by a phosphorus atom, etc. Is mentioned.

As an atomic group coordinated by a carbon atom, for example, an aromatic hydrocarbon ring group (preferably having a carbon number of 6 to 30, more preferably a carbon number of 6 to 20, particularly preferably a carbon number of 6 to 14, such as benzene, And naphthalene, anthracene, phenanthrene, pentacene, pyrene, perylene, and triphenylene), an unsaturated hydrocarbon group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 carbon atoms). -14, and examples thereof include vinyl and phenylacetylene), heterocyclic groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms. Furan, thiophene, pyrrole, imidazole, pyrazole, thiazole, oxazole, triazole, pyridine, pyra And fused rings containing these (eg indole, benzofuran, benzothiophene, benzimidazole, benzoxazole, benzthiazole, imidazopyridine, purine, quinoline, quinoxaline, phthalazine, phenanthroline) , Carbazole, tribenzazepine, indolenine, pyrrolotriazole, pyrrolopyrrole, pyrazolotriazole, and purine)) and their tautomers. These groups may further have a substituent. As an example of a substituent, group ^demonstrated by R ^{< a1>} , R ^<a2> in the below-mentioned general formula (IA) is mentioned.

  As an atomic group coordinated with a nitrogen atom, for example, an amino group (alkylamino group (preferably having 1 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, , Dimethylamino, etc.), arylamino groups (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, such as phenylamino, naphthylamino, and Diphenylamino, etc.), heterocyclic amino groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as aminofuran, aminothiophene, amino Pyrrole, aminoimidazole, aminopyrazole, aminothiazole, aminooxazole, aminotriazole Aminopyridine, aminopyrazine, aminopyrimidine, aminopyridazine, and aminotriazine, etc.) and condensed rings containing these (eg, aminoindole, aminobenzofuran, aminobenzothiophene, aminobenzimidazole, aminobenzoxazole, aminobenzthiazole) , Aminoimidazopyridine, aminopurine, aminoquinoline, aminoquinoxaline, aminophthalazine, aminophenanthroline, aminocarbazole, aminotribenzazepine, and aminoindolenine) and their tautomers. ),

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, benzoylamino, etc.), an alkoxycarbonylamino group (preferably Has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, and an aryloxycarbonylamino group (preferably 7 to 7 carbon atoms). 30, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino, etc.), sulfonylamino groups (preferably 1 to 30 carbon atoms, more preferably carbon atoms) 1 to 20, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino Benzenesulfonylamino, tolylsulfonylamino, etc.), nitrile group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, cyanide, acetonitrile , Benzonitrile, etc.), nitrogen-containing heterocyclic groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as pyrrole, imidazole, And pyrazole, thiazole, oxazole, triazole, pyridine, pyrazine, pyrimidine, pyridazine, and triazine, etc.) and condensed rings containing these (for example, indole, benzimidazole, benzoxazole, benzthiazole, imidazopyridine, purine, quinoline, Keno Sarin, phthalazine, phenanthroline, carbazole, tribenzazepine, indolenine, pyrrolotriazole, pyrrole, pyrazolotriazole, and purine and the like.), And tautomers thereof. These groups may further have a substituent. As an example of a substituent, group ^demonstrated by R ^{< a1>} , R ^<a2> in the below-mentioned general formula (IA) is mentioned.

As an atomic group coordinated by an oxygen atom, for example, an alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, such as methoxy, ethoxy, butoxy, 2-ethylhexyloxy, cyclohexyloxy, etc.), alkenyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as vinyloxy An aryloxy group (preferably having 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 20 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2- Naphtyloxy, 2-biphenyloxy, 3-biphenyloxy, 4-biphenyloxy, and 2,6-diphenyl A heterocyclic oxy 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 pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy). , Furyloxy, thienyloxy, benzofuranoxy, benzothiophenoxy, etc.), acyloxy groups (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms). For example, acetoxy, benzoyloxy, etc.), silyloxy groups (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyloxy, tri Phenylsilyloxy and dimethylpheny Such oxy and the like.), A carbonyl group (such as a ketone group, an ester group or an amide group), ether group (e.g. a dialkyl ether group, a diaryl ether or furyl group,), and the like. These groups may be further substituted. As an example of a substituent, group ^demonstrated by R ^{< a1>} , R ^<a2> in the below-mentioned general formula (IA) is mentioned.

As an atomic group coordinated with a sulfur atom, for example, 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, ethylthio and the like. An arylthio group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio and naphthylthio), a heterocyclic thio group (Preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, and 2-benz Thiazolylthio, etc.), thiocarbonyl groups (eg thioketone groups, thioester groups, etc.), thioethers (E.g. dialkyl thioether group, diaryl thioether or thiofuryl group, etc.,) and the like. These groups may be further substituted. As an example of a substituent, group ^demonstrated by R ^{< a1>} , R ^<a2> in the below-mentioned general formula (IA) is mentioned.

As an atomic group coordinated by a phosphorus atom, for example, a dialkylphosphino group (preferably having 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as dimethylphosphino, And diarylphosphino group (preferably having 12 to 50 carbon atoms, more preferably 12 to 40 carbon atoms, and particularly preferably 12 to 30 carbon atoms, such as diphenylphosphino). ), Trialkylphosphine (preferably having 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, particularly preferably 3 to 12 carbon atoms, such as trimethylphosphine, triethylphosphine, and tolbutylphosphine. Triarylphosphine (preferably having 18 to 50 carbon atoms, and more). Mashiku is 18 to 40 carbon atoms, and particularly preferably 18 to 30 carbon atoms, such as triphenyl phosphine, for example.), Phosphinine group and the like. These groups may be further substituted. As an example of a substituent, group ^demonstrated by R ^{< a1>} , R ^<a2> in the below-mentioned general formula (IA) is mentioned.

As an atomic group coordinated to M ¹ represented by L ¹¹ , L ¹² , L ¹³ , and L ¹⁴ , an atomic group coordinated with a carbon atom, an atomic group coordinated with a nitrogen atom, and coordinated with an oxygen atom An atomic group coordinated by a phosphorus atom, an atomic group coordinated by a carbon atom, an atomic group coordinated by a nitrogen atom, an atomic group coordinated by an oxygen atom are more preferable, and coordinated by a carbon atom An aryl group, a heteroaryl group coordinated with a carbon atom, a heteroaryl group coordinated with a nitrogen atom, an alkenyloxy group coordinated with an oxygen atom, an aryloxy group coordinated with an oxygen atom, coordinated with an oxygen atom More preferred are a silyloxy group, a carbonyl group coordinated by an oxygen atom, a carboxyl group coordinated by an oxygen atom, an acyl group coordinated by an oxygen atom, and a heteroaryloxy group coordinated by an oxygen atom, and coordinate by a carbon atom Aryl group, coordinated heteroaryl group at a carbon atom, and is coordinated heteroaryl group with nitrogen atoms particularly preferred.

Y ¹¹ and Y ¹² each represent a linking group. The linking group is not particularly limited, but includes an alkylene group (for example, a methylene group, a dimethylmethylene group, a diisopropylmethylene group, a diphenylmethylene group, an ethylene group, a tetramethylethylene group, and a trimethylene group), an alkenylene group ( For example, a vinylene group, a dimethyl vinylene group, etc.), an alkynylene group (for example, an ethynylene group, etc.), an arylene group (for example, a phenylene group, a naphthylene group, an anthracenylene group, etc.), a heteroarylene group, etc. are mentioned. (For example, a pyridylene group, a pyradylene group, a quinolylene group, etc.), an oxygen linking group, a sulfur linking group, a nitrogen linking group (for example, a methylamino linking group, a phenylamino linking group, a t-butylamino linking group, etc.). ), Lee-containing linking group (such as dimethyl silyl linking group, diphenyl silyl linking group, and, like the linking group (e.g., ethyleneoxy groups that combine these.), And the like.

Examples of the linking group represented by Y ¹¹ and Y ¹² include an alkylene group, an alkenylene group, an arylene group, a heteroarylene group, an oxygen linking group, a sulfur linking group, a nitrogen linking group, a silicon linking group, and a linking group thereof. A linking group combining an alkylene group and an oxygen linking group, a linking group combining an arylene group, an alkylene group and an oxygen linking group, and a linking group combining a heteroarylene group, an alkylene group and an oxygen linking group are more preferable.
Y ¹¹ and Y ¹² may have a substituent, and examples of the substituent include groups described for R ^a1 and R ^a2 in the general formula (IA) described later.

Specific examples of the linking group represented by Y ¹¹ and Y ¹² include the following.

The bond between M ^{1 and} L ^11, the bond between M ^{1 and} L ¹² , the bond between M ^{1 and} L ^13, and the bond between M ^{1 and} L ¹⁴ may be covalent bonds or coordinate bonds. There may be an ionic bond.

Among the compounds represented by formula (I), a compound represented by the following following general formula (I-A).

In general formula (IA), Y ^a1 and Y ^a2 each represent a linking group having the above structure . R ^a1 and R ^a2 each have, as a substituent , an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aromatic heterocyclic group having 1 to 12 carbon atoms, a fluorine atom, or 1 to 10 carbon atoms. An alkoxy group, an aryloxy group having 6 to 14 carbon atoms, an aromatic heterocyclic oxy group having 1 to 12 carbon atoms, a cyano group, or an amino group having 0 to 20 carbon atoms . m ^a1 and m ^a2 each represent an integer of 0 to 6. Xa represents a sulfonate ion, a perchlorate ion, a borate ion, or a phosphate ion . n represents a number of 0 or more determined so that the compound represented by the general formula (IA) is a neutral molecule.

The linking group represented by Y ^a1 and Y ^a2 has the same meaning as Y ¹¹ and Y ¹² in formula (I), and the preferred range is also the same.
Examples of the substituent represented by R ^a1 and R ^a2 include an alkyl 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 methyl and ethyl). , N-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like, and an alkenyl group (preferably). Has 2 to 30 carbon atoms, 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.), An alkynyl group (preferably Has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 2 to 10 carbon atoms. And an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms, such as phenyl and p-methylphenyl). , Naphthyl, anthranyl, biphenyl, etc.), an amino group (preferably having 0 to 40 carbon atoms, more preferably 0 to 30 carbon atoms, particularly preferably 0 to 20 carbon atoms, such as amino, methylamino , Dimethylamino, diethylamino, dibenzylamino, diphenylamino, and ditolylamino), 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). For example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy, etc. An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy, And a heterocyclic oxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms such as furyloxy, thienyloxy, Pyridyloxy, pyrazyloxy, pyrimidyloxy, quinolyloxy, etc.), acyl groups (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms such as acetyl, Benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably 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 and ethoxycarbonyl. ),

An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 14 carbon atoms, such as phenyloxycarbonyl), acyloxy group (preferably carbon 2 to 30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetoxy and benzoyloxy), acylamino group (preferably 2 to 30 carbon atoms, more preferably Has 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetylamino, benzoylamino and the like, and an alkoxycarbonylamino group (preferably 2 to 30 carbon atoms, more preferably 2 carbon atoms). -20, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino An aryloxycarbonylamino group (preferably having 7 to 30 carbon atoms, more preferably 7 to 20 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino). A sulfonylamino group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfonylamino and benzenesulfonylamino), a sulfamoyl group ( Preferably it is C0-30, More preferably, it is C0-20, Most preferably, it is C0-12, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc. are mentioned. ), A carbamoyl group (preferably having 1 to 30 carbon atoms, more preferably C1-C20, Most preferably, it is C1-C12, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl etc.), an alkylthio group (preferably C1-C30, more preferably C1-C20, Especially preferably, it is C1-C12, for example, methylthio, ethylthio etc. are mentioned, for example, An arylthio group (Preferably C6-C30, More preferably C6-C20, Especially preferable) Has 6 to 12 carbon atoms, for example, phenylthio and the like, and a heterocyclic thio group (preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms). For example, pyridylthio, 2-benzimidazolylthio, 2-benzoxazolylthio, 2-benzthiazo And rilthio. ), A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms,

Examples thereof include mesyl and tosyl. ), A sulfinyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), a ureido group (preferably Has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, phenylureido and the like, and a phosphoric acid amide group (preferably carbon). 1 to 30, more preferably 1 to 20 carbon atoms, 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 or iodine atom), cyano group, sulfo group, carboxyl group A nitro group, a hydroxamic acid group, a sulfino group, a hydrazino group, an imino group, a 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 and an oxygen atom A sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, carbazolyl, azepinyl, and the like, and a silyl group (preferably). ) Has 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl, triphenylsilyl, and di-tert-butylmethylsilyl). Group (preferably having 3 to 40 carbon atoms, more preferably Prime 3-30, particularly preferably from 3 to 24 carbon atoms, for example trimethylsilyloxy, etc. triphenylsilyl oxy and the like.) And the like. These substituents may be further substituted.

  The substituent is preferably an alkyl group, an aryl group, an aromatic heterocyclic group, a halogen atom, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a cyano group, or an amino group, more preferably an alkyl group or an aryl group. Group, aromatic heterocyclic group, fluorine atom, alkoxy group, aryloxy group, heterocyclic oxy group, cyano group, or amino group, more preferably an alkyl group having 1 to 10 carbon atoms, or 6 to 12 carbon atoms. An aryl group, an aromatic heterocyclic group having 1 to 12 carbon atoms, a fluorine atom, an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aromatic heterocyclic oxy group having 1 to 12 carbon atoms, A cyano group or an amino group having 0 to 20 carbon atoms, particularly preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, or 1 to 12 carbon atoms. Nitrogen-containing aromatic heterocyclic group, fluorine atom, alkoxy group having 1 to 10 carbon atoms, aryloxy group having 6 to 14 carbon atoms, aromatic heterocyclic oxy group having 1 to 12 carbon atoms, cyano group, or 2 carbon atoms ~ 20 amino groups.

m ^a1 and m ^a2 each represent an integer of 0 to 6, preferably 0 to 2, more preferably 0 or 1, and still more preferably 0. . When m ^a1 and m ²² are integers of 2 to 6, a plurality of R ^a1 and R ^a2 may be the same or different.

The anion represented by Xa may be either organic or inorganic. For example, halide ions (for example, Cl ⁻ , Br ⁻ , I ^{− and the} like), sulfonate ions (for example, trifluoromethane sulfonate, p-toluene sulfonate, benzene sulfonate) , Or parachlorobenzene sulfonate), sulfate ions (eg, methyl sulfate, ethyl sulfate, etc.), perchlorate, borate ions (eg, tetrafluoroborate, tetraphanyl borate, etc.), phosphate ions (eg, hexafluorophosphate, etc.), Acetate ions (for example, acetate, trifluoroacetate, picolinate, etc.), sulfonate ions, perchlorate ions, borate ions, or phosphate ions are preferred. Toion, phosphate ion is more preferable.
n represents a number of 0 or more determined so that the compound represented by the general formula (IA) is a neutral molecule, and when the central complex part is neutral, and the central complex part is a cation. In the case of forming an inner salt with a substituent and / or a linking group, n = 0.

Next, the compound represented by formula (II) will be described in detail.
The metal represented by M ² is not particularly limited, but is preferably 0 to 4 valence, more preferably 1 to 3 valence. Specific examples of the metal represented by M ² include Li, Be, Mg, Ba, Al, Ca, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Ag, W, Re, Os. , Ir, Pt, Au, Eu, Tb, and Yb. Preferably, as a metal, when the compound represented by the general formula (II) is used as a hole transport material (hole injection material, hole transport material, electron blocking material, light emitting layer host material, etc.), Cu, Ru, Rh, Pd, Ir, and Pt, more preferably Cu and Pt, and particularly preferably Pt. When the compound represented by the general formula (II) is used as an electron transport material (electron injection material, electron transport material, hole blocking layer, light emitting layer host material, etc.), Be, Mg, Al, Zn, Ga, Ru , Rh, Pd, and Pt are preferable, Zn and Pt are more preferable, and Pt is particularly preferable. Further, when the compound represented by the general formula (II) is used as a light emitting material, Cu, Ru, Rh, Pd, Re, Ir, and Pt are preferable, Ru, Rh, Pd, Re, and Pt are more preferable, Pt is particularly preferred.

The atomic groups coordinated to M ² represented by L ²¹ , L ²² , L ²³ and L ²⁴ are respectively synonymous with L ^{11 to} L ¹⁴ in the general formula (I).
L ²¹ , L ²² and L ²³ are preferably the same as those exemplified as the preferred atomic group of L ^{11 to} L ¹⁴ in the general formula (I).
The atom coordinating groups M ² represented by L ^24, as the L ^24, atom coordinating group with carbon atoms, atom coordinating group with a nitrogen atom, atom coordinating group with an oxygen atom, a sulfur An atom group coordinated by an atom and an atom group coordinated by a phosphorus atom are preferred, an atom group coordinated by a carbon atom, an atom group coordinated by a nitrogen atom, an atom group coordinated by an oxygen atom, and a sulfur atom. A more preferred group of atoms is an aryl group coordinated by carbon atom, heteroaryl group coordinated by carbon atom, heteroaryl group coordinated by nitrogen atom, carboxyl group coordinated by oxygen atom, coordinated by oxygen atom More preferred are an aryloxy group that is coordinated, a heteroaryloxy group that is coordinated with an oxygen atom, a silyloxy group that is coordinated with an oxygen atom, an arylthio group that is coordinated with a sulfur atom, and a heteroarylthio group that is coordinated with a sulfur atom, original In coordinating an aryloxy group, coordinating heteroaryloxy group with an oxygen atom it is particularly preferred.

Y ²¹ and Y ²² have the same meanings as Y ¹¹ and Y ¹² in the general formula (I), respectively, and preferred ranges thereof are also the same.

The bond between M ^{2 and} L ^21, the bond between M ^{2 and} L ²² , the bond between M ^{2 and} L ^23, and the bond between M ^{2 and} L ²⁴ may be a covalent bond or a coordinate bond. There may be an ionic bond.

  Of the compounds represented by the general formula (II), a compound represented by the following general formula (II-A) is preferable.

In general formula (II-A), Y ^b1 and Y ^b2 each represent a linking group having the above structure . R ^b1 , R ^b2 , R ^b3, and R ^b4 are each a substituent having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aromatic heterocyclic group having 1 to 12 carbon atoms, or a fluorine atom. Represents an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aromatic heterocyclic oxy group having 1 to 12 carbon atoms, a cyano group, or an amino group having 0 to 20 carbon atoms . m ^b1 , m ^b2 , m ^b3 , and m ^b4 each represents an integer of 0 to 3.

The linking group represented by Y ^b1 and Y ^b2 has the same meaning as Y ¹¹ and Y ¹² in formula (I), and the preferred range is also the same.
The substituents represented by R ^b1 , R ^b2 , R ^b3 , and R ^b4 have the same meanings as R ^a1 and R ^a2 in formula (IA), and preferred ranges are also the same.
m ^b1 , m ^b2 , m ^b3 , and m ^b4 are preferably 0 to 2, more preferably 0 or 1, and still more preferably 0. When m ^b1 , m ^b2 , m ^b3 , and m ^b4 are 2 or 3, the plurality of R ^b1 , R ^b2 , R ^b3 , and R ^b4 may be the same or different.

Next, the compound represented by formula (III) will be described in detail.
Although the metal represented by M ³ is not particularly limited, it is preferably 0 to 4 valent, more preferably 1 to 3 valent. Specific examples of the metal represented by M ³ include Li, Be, Mg, Ba, Al, Ca, Fe, Co, Ni, Cu, Zn, Ga, Ru, Rh, Pd, Ag, W, Re, Os. , Ir, Pt, Au, Eu, Tb, and Yb. Preferably, as a metal, when the compound represented by the general formula (III) is used as a hole transporting material (hole injection material, hole transport material, electron blocking material, light emitting layer host material, etc.), Cu, Ru, Rh, Pd, Ir, and Pt, more preferably Cu and Ir, and particularly preferably Ir. When the compound represented by the general formula (III) is used as an electron transport material (electron injection material, electron transport material, hole blocking material, light emitting layer host material, etc.), Be, Mg, Al, Zn, Ga, Ru , Rh, Pd, and Pt are preferable, Al, Ga, and Pt are more preferable, and Pt is particularly preferable. Further, when the compound represented by the general formula (III) is used as the light emitting material, Cu, Ru, Rh, Pd, Re, Ir, and Pt are preferable, and Ru, Rh, Pd, Re, Ir, and Pt are preferable. More preferably, Re, Ir, and Pt are more preferable, and Ir is particularly preferable.

  Of the compounds represented by the general formula (III), a compound represented by the following general formula (III-A) is preferable.

In general formula (III-A), Y ^c1 and Y ^c2 each represent a linking group having the above structure . R ^c1 , R ^c2 , R ^c3 , R ^c4 , R ^c5 and R ^c6 are each a substituent having 1 to 10 carbon atoms, an alkyl group having 6 to 12 carbon atoms, or an aromatic group having 1 to 12 carbon atoms. Heterocyclic group, fluorine atom, C 1-10 alkoxy group, C 6-14 aryloxy group, C 1-12 aromatic heterocyclic oxy group, cyano group, or C 0-20 amino Represents a group . m ^c1 , m ^c2 , m ^c3 , m ^c4 , m ^c5 and m ^c6 each represents an integer of 0 to 3.

The linking group represented by Y ^c1 and Y ^c2 has the same meaning as Y ¹¹ and Y ¹² in formula (I), and the preferred range is also the same.
The substituents represented by R ^c1 , R ^c2 , R ^c3 , R ^c4 , R ^c5 , and R ^{c6 have the same definitions} as R ^a1 and R ^a2 in general formula (IA), and the preferred ranges are also the same. is there.
As m ^c1 , m ^c2 , m ^c3 , m ^c4 , m ^c5 , and m ^c6 , 0 to 2 are preferable, 0 or 1 is more preferable, and 0 is still more preferable. When m ^c1 , m ^c2 , m ^c3 , m ^c4 , m ^c5 , and m ^c6 are 2 or 3, the plurality of R ^c1 , R ^c2 , R ^c3 , R ^c4 , R ^c5 , and R ^c6 are the same. Or different.

  Next, specific examples of the interlock type compound used in the present invention are shown, but the present invention is not limited thereto.

<Synthesis Method of Interlock Type Compound>
As a typical synthesis method of an interlock type compound, there are a so-called template method and a self-assembly method. The template method uses multiple interactions such as coordination bonds, donor-acceptor interactions, and hydrogen bonds to attract multiple chain molecules or cyclic molecules and chain molecules to cyclize the chain molecules. This is a method of creating an interlock skeleton. The self-assembly method is a method of designing a skeleton in which the interlock structure is thermodynamically stable, and then using reversible bond generation to generate the interlock as a result of thermodynamic equilibrium. This is a method for obtaining a lock-type compound.
The interlock type compound used in the present invention is, for example, Angew. Chem. Int. Ed. Engl. 28, 189 (1989), Angew. Chem. , Int. Ed. Engl. , 32, 1434 (1993), J. Am. Am. Chem. Soc. 116, 375 (1994); Chem. Soc. , Chem. Commun. , 2231 (1994), Angew. Chem. , Int. Ed. Engl. 36, 1308 (1997), J. Am. Chem. Soc. , Chem. Commun. , 2053 (1997) and references cited therein and the like.

<Application>
In the present invention, the interlock type compound can be used as a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron block layer, a hole block layer, or the like.
The preferred layer used depends on the design of the interlock type compound, but in the case of a metal complex type interlock type compound, it is preferably used for the hole injection layer, the light emitting layer, the electron transport layer, or the electron injection layer. It is preferable to use for a hole injection layer and a light emitting layer.

<How to use>
In the present invention, the method for forming a layer containing an interlock type compound is not particularly limited, but a resistance heating vapor deposition method, an electron beam method, a sputtering method, a molecular lamination method, a wet coating method ( _{spray coating method). Dip coating method, impregnation method, roll coating method, gravure coating method, reverse coating method, roll brush method, air knife coating method, curtain coating method, spin coating method, flow coating method, bar coating method, micro gravure coating method, Air doctor coating, blade coating method, squeeze coating method, transfer roll coating method, kiss coating method, cast coating method, extrusion coating method, wire bar coating method, screen coating method, etc.)} , inkjet method, printing method, or transfer method Such a method is used. In the present invention, since the interlock type compound can be dissolved in a solvent at a high concentration, a wet coating method can be preferably used.

  The concentration of the interlock type compound in the case of producing by a coating method is not particularly limited, but is preferably 0.0001% by mass to 90% by mass, more preferably 0.001% by mass to 70% by mass. More preferably, it is 0.01 mass% or more and 50 mass% or less, Most preferably, it is 0.1 mass% or more and 30 mass% or less.

  In the case of the coating method, the solvent to be used is not particularly limited, but preferably, for example, an aromatic hydrocarbon type (for example, benzene, toluene, ethylbenzene, xylene, or chlorobenzene), a halogenated hydrocarbon type (for example, dichloroethane, chloroform, etc.), Ether type (eg, tetrahydrofuran, dioxane, etc.), Amide type (eg, dimethylformamide, dimethylacetamide, etc.), Ester type (eg, ethyl acetate), Alcohol type (eg, methanol), Ketone type (eg, acetone, methyl ethyl ketone, cyclohexanone, etc.) , Sulfoxide (for example, dimethyl sulfoxide), nitrile (for example, acetonitrile) and the like. These solvents may be used alone or in combination of two or more.

  As a method of coating, a method of coating by dissolving or dispersing the interlock type compound in a solvent (for example, those mentioned as examples of the wet coating method can be applied), an inkjet method, a printing 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, in the case of the coating method, the above materials may be dissolved or dispersed together with the resin component to prepare a coating solution. As resin components, polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, Ethyl cellulose, polyvinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicon resin, or the like can be used.

<Film thickness>
When the interlock type compound is used for the hole injection layer, the film thickness is not particularly limited, but is usually preferably 1 nm to 2 μm, more preferably 5 nm to 500 nm, and particularly preferably 10 nm to 500 nm. When the film thickness is thinner than 1 nm, a short circuit occurs due to the unevenness of the electrodes, and problems such as luminance unevenness occur. Also, when the film thickness is thicker than 2 μm, problems such as an increase in driving voltage occur.
When the interlock type compound is used for the hole transport layer, the film thickness is not particularly limited, but is usually preferably 1 nm to 500 nm, more preferably 3 nm to 300 nm, and particularly preferably 5 nm to 100 nm.
When the film thickness is thinner than 1 nm, a short circuit occurs due to the unevenness of the electrodes, and problems such as luminance unevenness occur. Moreover, when the film thickness is thicker than 500 nm, problems such as an increase in driving voltage occur.
When the interlock type compound is used for the light emitting layer, the film thickness is not particularly limited, but is usually preferably 5 nm to 1 μm, more preferably 10 nm to 100 nm, and particularly preferably 20 nm to 80 nm.
When the interlock type compound is used for the electron transport layer, the film thickness is not particularly limited, but is usually preferably 1 nm to 1 μm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 60 nm.
When the interlock type compound is used for the electron injection layer, the film thickness is not particularly limited, but is usually preferably 1 nm to 1 μm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 60 nm.
The above film thickness is preferable in terms of achieving both driving voltage, light emission efficiency, and durability.

2. Components of Organic Electroluminescent Device Next, the components that constitute the luminescent material of the present invention will be described in detail.

<Board>
The substrate used in the present invention is preferably a substrate that does not scatter or attenuate light emitted from the organic compound layer. Specific examples include zirconia-stabilized yttrium (YSZ), inorganic materials such as glass, polyesters such as polyethylene terephthalate, polybutylene phthalate, and polyethylene naphthalate, polystyrene, polycarbonate, polyethersulfone, polyarylate, polyimide, and polycycloolefin. , Norbornene resins, and organic materials such as 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 has a function as an electrode for supplying holes to the organic compound layer, and there is no particular limitation on the shape, structure, size, etc., depending on the use and purpose of the light-emitting element. , Can be appropriately selected from 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 described in detail in the book “New Development of Transparent Electrode Films” published by CMC (1999), supervised by Yutaka Sawada, 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 compound 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.

  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 and ytterbium. 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% by mass to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Etc.).

  The materials for the cathode are described in detail in JP-A-2-15595 and JP-A-5-121172, and the materials described in these public relations 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 formation position is not particularly limited, and may be formed on the entire organic compound 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 compound layer with a thickness of 0.1 nm 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 nm to 10 nm and further laminating a transparent conductive material such as ITO or IZO.

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

-Formation of organic compound layer-
In the organic electroluminescence device of the present invention, each layer constituting the organic compound layer is preferably formed by any of dry film forming methods such as vapor deposition and sputtering, wet coating methods, transfer methods, printing methods, and ink jet methods. be able to.

-Organic light emitting layer-
The organic 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 having a function of providing a field to emit light.
The light emitting layer in the present invention may be composed of only 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 dopant may be one type or two or more types. The host material is preferably a charge transport material. The host material may be one type or two or more types, and examples thereof include a configuration in which an electron transporting host material and a hole transporting host material are mixed. Further, the light emitting layer may include a material that does not have charge transporting properties and does not emit light.
Further, the light emitting layer may be a single layer or two or more layers, and each layer may emit light in different emission colors.
As the light emitting material that can be used in the present invention, other fluorescent light emitting materials and phosphorescent light emitting materials can be used in addition to the interlock type compound of the present invention. These light emitting materials used in combination may be a low molecular compound or a high molecular compound.

  Examples of fluorescent materials that can be used in the present invention include, for example, benzofuran derivatives, benzothiophene derivatives, pyran derivatives, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetra Phenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, condensed aromatic compounds, perylene derivatives, oxadiazole derivatives, oxazine derivatives, aldazine derivatives, pyrazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiols Asiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, diketopyrrolopyrrole derivatives, aromatic dimethylidin compounds , 8-quinolinol derivatives of various metal complexes typified by metal complexes of the metal complex and pyrromethene derivatives, polythiophene, polyphenylene, polyphenylene vinylene polymer compounds include compounds such as organic silane derivatives.

Examples of the phosphorescent material that can be used in the present invention include complexes containing transition metal atoms or lanthanoid atoms.
Although it does not specifically limit as a transition metal atom, Preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, and platinum are mentioned, More preferably, they are rhenium, iridium, and platinum.
Lanthanoid atoms include lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Among these lanthanoid atoms, neodymium, europium, and gadolinium are preferable.

Examples of the ligand of the complex include G.I. WIlkInson et al., ComprehensIve CoordInatIon ChemIstry, published by Pergamon Press, 1987, H.C. YersIn, “Photochemistry and Photophysics of CoordInatIon Compounds”, published by SprInger-Verlag, Inc., 1987, Akio Yamamoto, “Organic Metal Chemistry-Fundamentals and Applications,” published by Soukabo, Inc., published in 1982, etc. .
The specific ligand is preferably a halogen ligand (preferably a chlorine ligand), an aromatic ligand (eg, cyclopentadienyl anion, benzene anion, or naphthyl anion), nitrogen-containing Heterocyclic ligands (eg, phenylpyridine, benzoquinoline, quinolinol, bipyridyl, or phenanthroline), diketone ligands (eg, acetylacetone), carboxylic acid ligands (eg, acetate ligands), alcohols A ligand (such as a phenolate ligand), a carbon monoxide ligand, an isonitrile ligand, or a cyano ligand, more preferably a nitrogen-containing heterocyclic ligand. The complex may have one transition metal atom in the compound, or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.

  The phosphorescent material is preferably contained in the light emitting layer in an amount of 0.1% by mass to 40% by mass, and more preferably 0.5% by mass to 20% by mass.

  Examples of the host material contained in the light emitting layer in the present invention include those having a pyrrole skeleton, those having an indole skeleton, those having a carbazole skeleton, those having a diarylamine skeleton, those having a pyridine skeleton, pyrazine Examples thereof include those having a skeleton, those having a triazine skeleton, those having an arylsilane skeleton, and materials exemplified in the sections of a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer described later.

  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.

-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. As a material that can be used for the hole injection layer and the hole transport layer of the present invention, other hole injection materials and hole transport materials can be used in addition to the interlock type compound of the present invention. These hole injection material and hole transport material may be a low molecular compound or a high molecular compound.
Specifically, pyrrole derivatives, carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styryl Anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, phthalocyanine compounds, porphyrin compounds, thiophene derivatives, organosilane derivatives, or carbon , Etc. are preferable.

  An electron-accepting dopant can be contained in the hole injection layer or the hole transport layer of the organic EL device of the present invention. As the electron-accepting dopant introduced into the hole-injecting layer or the hole-transporting layer, an inorganic compound or an organic compound can be used as long as it has an electron-accepting property and oxidizes an organic compound.

  Specifically, examples of the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, metal oxides such as vanadium pentoxide, and molybdenum trioxide.

In the case of an organic compound, a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
In addition, JP-A-6-212153, JP-A-11-111463, JP-A-11-251067, JP-A-2000-196140, JP-A-2000-286054, JP-A-2000-315580, JP-A-2001-102175, JP-A-2001-2001. -160493, JP2002-252085, JP2002-56985, JP2003-157981, JP2003-217862, JP2003-229278, JP2004-342614, JP2005-72012, JP20051666667 The compounds described in JP-A-2005-209643 and the like can be preferably used.

  These electron-accepting dopants may be used alone or in combination of two or more. Although the usage-amount of an electron-accepting dopant changes with kinds of material, it is preferable that it is 0.01 mass%-50 mass% with respect to hole transport layer material, and it is 0.05 mass%-20 mass%. It is further more preferable and it is especially preferable that it is 0.1 mass%-10 mass%.

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 materials described above, 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. As a material that can be used for the electron injection layer and the electron transport layer of the present invention, in addition to the interlock type compound of the present invention, other hole injection materials and hole transport materials can be used. These hole injection material and hole transport material may be a low molecular compound or a high molecular compound.
Specifically, pyridine derivatives, quinoline derivatives, pyrimidine derivatives, pyrazine derivatives, phthalazine derivatives, phenanthroline derivatives, triazine derivatives, 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, naphthalene, perylene and other aromatic ring tetracarboxylic acid anhydrides, phthalocyanine derivatives, 8-quinolinol derivative metal complexes, Metal phthalocyanines, various metal complexes represented by metal complexes with benzoxazole and benzothiazole as ligands, organosilane derivatives represented by siloles Body, or the like is preferably a layer containing.

The electron injection layer or the electron transport layer of the organic EL device of the present invention can contain an electron donating dopant. The electron donating dopant introduced into the electron injecting layer or the electron transporting layer only needs to have an electron donating property and a property of reducing an organic compound, such as an alkali metal such as Li or an alkaline earth metal such as Mg. Transition metals including rare earth metals and reducing organic compounds are preferably used. As the metal, a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd , And Yb. Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds.
In addition, materials described in JP-A-6-212153, JP-A-2000-196140, JP-A-2003-68468, JP-A-2003-229278, JP-A-2004-342614, and the like can be used.

  These electron donating dopants may be used alone or in combination of two or more. The amount of the electron donating dopant varies depending on the type of material, but is preferably 0.1% by mass to 99% by mass, and 1.0% by mass to 80% by mass with respect to the electron transport layer material. Is more preferable, and 2.0 mass% to 70 mass% is particularly preferable.

The thicknesses of the electron injection layer and the electron transport layer are each preferably 500 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 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.

-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 compound layer adjacent to the light emitting layer on the cathode side.
Examples of the compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such 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 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.

-Electronic block layer-
The electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing through to the anode side. In the present invention, an electron blocking layer can be provided as the organic compound layer adjacent to the light emitting layer on the anode side.
As examples of the compound constituting the electron blocking layer, for example, those mentioned as the hole transport material described above can be applied.
The thickness of the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and even more preferably 10 nm to 100 nm.
The hole blocking 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.
<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 , TiO ₂ , metal nitrides such as SiN _x , SiN _x O _y , metal fluorides such as MgF ₂ , LiF, AlF ₃ , 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 Copolymer obtained by copolymerization, cyclic in the copolymer main chain Examples thereof include a fluorine-containing copolymer having a structure, a water-absorbing substance having a water absorption of 1% or more, and a moisture-proof substance having a water absorption of 0.1% or less.

  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, or transfer method can be applied.

<Sealing>
Furthermore, the organic electroluminescent element of this invention may seal the whole element using a sealing container.
Further, a moisture absorbent or an inert liquid may be sealed in a space between the sealing container and the light emitting 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 paraffins, liquid paraffins, fluorinated solvents such as perfluoroalkane, perfluoroamine, and perfluoroether, chlorinated solvents, and silicone oils. Can be mentioned.

<Drive>
The organic electroluminescence device of the present invention emits light by applying a direct current (which may include an alternating current component as necessary) voltage (usually 2 to 15 volts) or a direct current between the anode and the cathode. Obtainable.
The driving method of the organic electroluminescence device of the present invention is described in JP-A-2-148687, JP-A-6-301355, JP-A-5-29080, JP-A-7-134558, JP-A-8-234658, and JP-A-8-2441047. The driving method described in each publication, Japanese Patent No. 2784615, US Pat. Nos. 5,828,429, 6023308, and the like can be applied.

  The light-emitting element of the present invention can improve the light extraction efficiency by various known devices. For example, by processing the substrate surface shape (for example, forming a fine concavo-convex pattern), controlling the refractive index of the substrate / ITO layer / organic layer, controlling the film thickness of the substrate / ITO layer / organic layer, etc. It is possible to improve light extraction efficiency and external quantum efficiency.

  The light-emitting element of the present invention may be a so-called top emission type in which light emission is extracted from the anode side.

(Use of the present invention)
The organic electroluminescence device of the present invention can be suitably used for display devices, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

The present invention will be specifically described using examples, but the present invention is not limited to these examples.
Example 1
<Production of organic EL element>
(Preparation of the organic EL device 1 of the present invention)
1) Formation of anode A transparent support substrate was formed by depositing ITO on a glass substrate of 25 mm × 25 mm × 0.7 mm to a thickness of 150 nm to form a film (Tokyo Sanyo Vacuum Co., Ltd.). This transparent support substrate was etched and washed.
2) Hole injection / transport layer On this ITO glass substrate, Baytron P (PEDOT-PSS solution (polyethylenedioxythiophene-polystyrenesulfonic acid doped body) / manufactured by Bayer) was spin-coated as a hole injection / transport layer. Thereafter, it was vacuum dried (film thickness of about 100 nm).

3) Light-Emitting Layer As a light-emitting material on the hole injection / transport layer, an interlock type compound No. A solution containing about 0.08% by mass of a light emitting material in which 3 mg of 17 and 40 mg of polyvinylcarbazole as a host material were dissolved in 3.5 g of 1,2-dichloroethane was spin-coated and then dried in vacuo. The film thickness was about 40 nm.

4) Electron transport layer Next, the electron transport materials BAlq and Alq were sequentially deposited so as to have film thicknesses of 20 nm (deposition rate 0.15 nm / second) and 30 nm (deposition rate 0.1 nm / second), respectively. did.
5) Electron injection layer Further, LiF was deposited to a thickness of about 1 nm (deposition rate: 0.01 nm / second).
6) Formation of cathode electrode A patterned mask (a mask having a light emitting area of 2 mm × 2 mm) was placed thereon, and aluminum was deposited to a thickness of about 70 nm (deposition rate: 0.3 nm / second) to produce a device. The produced element was sealed in a dry glove box.
Said vapor deposition was performed in the vacuum of 10 < ^-3 > Pa-10 < ^-4 > Pa, and the substrate temperature on the conditions of room temperature.

(Preparation of the organic EL element 2 of the present invention)
In the production of the organic EL device 1 of the present invention, the interlock type compound No. 1 in the light emitting layer was used. In place of Interlock Type Compound No. 17 A comparative organic EL element 2 was produced in exactly the same manner as in the present invention 1 except that 22 was used.
(Preparation of the organic EL device 3 of the present invention)
In the production of the organic EL device 1 of the present invention, the interlock type compound No. 1 in the light emitting layer was used. In place of Interlock Type Compound No. 17 A comparative organic EL device 3 was produced in exactly the same manner as in the present invention 1 except that 30 was used.
(Preparation of the organic EL element 4 of the present invention)
In the production of the organic EL device 1 of the present invention, the interlock type compound No. 1 in the light emitting layer was used. In place of Interlock Type Compound No. 17 A comparative organic EL device 4 was produced in exactly the same manner as in the present invention 1 except that 34 was used.

(Production of Comparative Organic EL Element A)
In the production of the organic EL device 1 of the present invention, the interlock type compound No. 1 in the light emitting layer was used. A comparative organic EL device A was prepared in exactly the same manner as the organic EL device 1 of the present invention except that Ir (ppy) ₃ was used instead of 17.

(Production of Comparative Organic EL Element B)
In the production of the organic EL device 1 of the present invention, the interlock type compound No. 1 in the light emitting layer was used. A comparative organic EL device B was produced in exactly the same manner as the organic EL device 1 of the present invention except that the compound PA (the compound described in Patent No. 2003-77675) was used instead of 17.

(Production of comparative organic EL element C)
In the production of the organic EL device 1 of the present invention, the interlock type compound No. 1 in the light emitting layer was used. A comparative organic EL device C was produced in exactly the same manner as in the organic EL device 1 of the present invention, except that compound P-B (the compound described in Japanese Patent Publication No. 2003-77675) was used instead of 17.

<Performance evaluation of organic EL elements>
1) External quantum efficiency A source measure unit 2400 manufactured by Toyo Technica Co., Ltd. is used to apply a direct current voltage to each element to emit light. The brightness was measured using a luminance meter BM-8 manufactured by Topcon Corporation. The emission spectrum and emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics. Based on these numerical values, the external quantum efficiency when the luminance was around 1000 cd / m ² was calculated by the luminance conversion method.

2) Maximum brightness Using a source measure unit 2400 manufactured by Toyo Technica Co., Ltd., a direct current voltage is applied to each element to emit light. The current flowing through the device was gradually increased, and the luminance immediately before the device breakdown was measured as the maximum luminance.
3) driving durability: a luminance half-life each element by applying a DC voltage so that the luminance 1000 cd / ^{m 2,} the time was measured until the brightness is 500 cd / ^{m 2.} This luminance half time was used as an index of driving durability.

4) Storage stability after production of organic EL device The luminance when the device was driven at a current density of 10 mA / cm ² immediately after production of the device was taken as 100, and the luminance after the device was stored at 75 ° C. for 24 hours was measured. The storage stability was evaluated by the value.

  The results obtained are summarized in Table 1 below.

  As is clear from the above results, the device of the present invention had higher maximum luminance, superior light emission efficiency, and driving durability than the comparative device. Moreover, the performance degradation after manufacturing the element was small, and the storage stability was excellent.

Example 2
<Production of element>
In the light emitting layer of Example 1, in the device 3 of the present invention and the device A for comparison, samples having different concentrations of the light emitting materials shown in Table 2 were prepared.
<Performance evaluation>
The results of evaluation in the same manner as in Example 1 are shown in Table 2.

In the comparative device, even when the Ir (ppy) ₃ concentration was increased, the maximum luminance and the external quantum efficiency were slightly increased, but rather the highest luminance and the external quantum efficiency tended to decrease at a high concentration. When the concentration was increased, the color was changed to yellowish green, and the emission color changed. Further, in the element 2-8 in which Ir (ppy) ₃ was made high in concentration, the light emitting surface was non-uniform in a streak shape.
On the other hand, in the device of the present invention, the maximum luminance, the external quantum efficiency increased and the durability increased as the concentration of the interlock type compound increased. The luminescent color hardly changed. Interlock type compound No. Even in the device 2-4 coated with 30 in a high concentration solution of 10% by mass, the light emitting surface was uniform, and it was found that the device fabricated by the wet coating method showed excellent performance.
Note that the change in emission color (lengthening of wavelength) at a high concentration of Ir (ppy) ₃ is predicted to accompany molecular association, but the interlock type compound used in the present invention is manufactured at a high concentration by coating. Even if the film is formed, it is considered that the molecule is dispersed in a monomeric manner and the emission color does not change.

Example 3
<Production of organic EL element>
(Preparation of organic EL device 3-1 of the present invention)
1) Formation of anode A transparent support substrate was formed by depositing ITO on a glass substrate of 25 mm × 25 mm × 0.7 mm to a thickness of 150 nm to form a film (Tokyo Sanyo Vacuum Co., Ltd.). This transparent support substrate was etched and washed.
2) Hole injection layer On this ITO glass substrate, an interlock type compound No. 1 was used as a hole injection layer. A solution (about 0.57% by mass) of 2 (20 mg) dissolved in 3.5 g of 1,2-dichloroethane was spin-coated and then vacuum-dried (film thickness: about 10 nm).

3) Hole transport layer α-NPD ((N, N′-di-α-naphthyl-N, N′-diphenyl) -benzidine) is formed as a hole transport layer on the hole injection layer with a film thickness of 30 nm ( Vapor deposition was performed at a deposition rate of 0.1 nm / second.
4) Light-Emitting Layer Ir (ppy) ₃ as a light-emitting material on the hole transport layer and CBP as a host material in a ratio (mass ratio) of 1:12 (film deposition rate: Ir (ppy) ₃ 0 (.02 nm / second, CBP 0.24 nm / second).

5) Electron transport layer Next, the electron transport materials BAlq and Alq were sequentially deposited to a film thickness of 20 nm (deposition rate 0.15 nm / second) and 30 nm (deposition rate 0.1 nm / second), respectively. did.
6) Electron injection layer Further, LiF was deposited to a thickness of about 1 nm (deposition rate: 0.01 nm / second).
7) Formation of cathode electrode A patterned mask (a mask having a light emitting area of 2 mm × 2 mm) was placed thereon, and aluminum was deposited to a thickness of about 70 nm (deposition rate: 0.3 nm / second) to produce a device. The produced element was sealed in a dry glove box.
Deposition was performed in a vacuum of 10 ⁻³ Pa to 10 ⁻⁴ Pa and a substrate temperature at room temperature.

(Production of Comparative Organic EL Element 3-2)
In the production of the organic EL device 3-1 of the present invention, the interlock type compound No. 1 in the hole injection layer was used. A comparative organic EL element 3-2 was produced in the same manner as the organic EL element 3-1 of the present invention except that 20 mg of copper phthalocyanine was used instead of 2.
In this case, the hole injection layer coating solution was hardly dissolved and applied in a suspended state.
(Production of Comparative Organic EL Element 3-3)
In the production of the organic EL device 3-1 of the present invention, the interlock type compound No. 1 in the hole injection layer was used. A comparative organic EL device 3-3 was produced in the same manner as the organic EL device 3-1 of the present invention except that 20 mg of m-MTDATA (arylamine compound) was used instead of 2.

<Performance evaluation of organic EL elements>
External quantum efficiency, driving durability, and storage stability were evaluated in the same manner as in Example 1.
The results obtained are summarized in Table 3 below.

  As is clear from the above results, copper phthalocyanine has low solubility in a solvent and does not emit light. The arylamine type hole injection material m-MTDATA can be applied, but has low storage stability. On the other hand, the device of the present invention can be formed by wet coating and has excellent storage stability.

Example 4
<Production of organic EL element>
(Preparation of organic EL element 4-1 of the present invention)
The 1) anode and 2) hole injection / transport layer were formed in the same manner as in Example 1.
3) Luminescent layer On the hole injection / transport layer, rubrene (8 mg) as a luminescent material, polyvinylcarbazole (30 mg) as a host material, and interlock type compound No. 1 as an electron transport material. A solution of 35 (10 mg) dissolved in 4.0 g of 1,2-dichloroethane was spin-coated and then dried in vacuo. The film thickness was about 40 nm.
4) Electron transport layer Next, the electron transport materials BAlq and Alq were sequentially deposited so as to have film thicknesses of 20 nm (deposition rate 0.15 nm / second) and 30 nm (deposition rate 0.1 nm / second), respectively. did.
5) Electron injection layer Further, LiF was deposited to a thickness of about 1 nm (deposition rate: 0.01 nm / second).
6) Formation of cathode electrode A patterned mask (a mask having a light emitting area of 2 mm × 2 mm) was placed thereon, and aluminum was deposited to a thickness of about 70 nm (deposition rate: 0.3 nm / second) to produce a device. The produced element was sealed in a dry glove box.
Deposition was performed in a vacuum of 10 ⁻³ Pa to 10 ⁻⁴ Pa and a substrate temperature at room temperature.
(Production of Comparative Organic EL Element 4-2)
In the production of the organic EL device 4-1 of the present invention, the interlock type compound No. 1 used as the electron transport material in the light emitting layer was used. A comparative organic EL element 4-2 was produced in the same manner as the organic EL element 4-1 of the present invention except that Bphen (10 mg) was used instead of 35.

<Performance evaluation of organic EL elements>
External quantum efficiency, driving durability, and storage stability were evaluated in the same manner as in Example 1.
The results obtained are summarized in Table 4 below.

  As is clear from the above results, the device of the present invention was superior in luminous efficiency and driving durability compared to the comparative device. Moreover, the performance degradation after manufacturing the element was small, and the storage stability was excellent.

Claims (7)

An organic electroluminescent device having at least one organic layer between a pair of electrodes, the compounds represented by the following general formulas (IA), (II-A) and (III-A), and the following compounds An organic electroluminescent device comprising at least one interlock compound selected from 1, 3, 5, 7, 9, 11, 13-16, 29, 31, 33, and 35-37 .







(In General Formula (IA), Y ^a1 and Y ^a2 each represent a linking group having the following structure: R ^a1 and R ^a2 each represent a substituent having 1 to 10 carbon atoms and 6 carbon atoms. -12 aryl group, C1-C12 aromatic heterocyclic group, fluorine atom, C1-C10 alkoxy group, C6-C14 aryloxy group, C1-C12 aromatic heterocycle Represents an oxy group, a cyano group, or an amino group having 0 to 20 carbon atoms, m ^a1 and m ^a2 each represent an integer of 0 to 6. Xa represents a sulfonate ion, a perchlorate ion, a borate ion, or a phosphate. Represents an ion, and n represents a number of 0 or more determined so that the compound represented by formula (IA) is a neutral molecule.
In general formula (II-A), Y ^b1 and Y ^b2 each represent a linking group having the following structure . R ^b1 , R ^b2 , R ^b3, and R ^b4 are each a substituent having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms, an aromatic heterocyclic group having 1 to 12 carbon atoms, or a fluorine atom. Represents an alkoxy group having 1 to 10 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, an aromatic heterocyclic oxy group having 1 to 12 carbon atoms, a cyano group, or an amino group having 0 to 20 carbon atoms . m ^b1 , m ^b2 , m ^b3 , and m ^b4 each represents an integer of 0 to 3.
In general formula (III-A), Y ^c1 and Y ^c2 each represent a linking group having the following structure . R ^c1 , R ^c2 , R ^c3 , R ^c4 , R ^c5 and R ^c6 are each a substituent having 1 to 10 carbon atoms, an alkyl group having 6 to 12 carbon atoms, or an aromatic group having 1 to 12 carbon atoms. Heterocyclic group, fluorine atom, C 1-10 alkoxy group, C 6-14 aryloxy group, C 1-12 aromatic heterocyclic oxy group, cyano group, or C 0-20 amino Represents a group . m ^c1 , m ^c2 , m ^c3 , m ^c4 , m ^c5 and m ^c6 each represents an integer of 0 to 3. )




  The organic electroluminescent element according to claim 1, wherein the layer containing the interlock type compound is a layer formed by a wet coating method. The organic electroluminescent device according to claim 2, wherein the concentration of the interlock type compound when applied by the wet coating method is 0.01 mass% or more and 50 mass% or less. The organic electroluminescent device according to any one of claims 1 to 3, wherein the layer containing the interlock type compound is a hole injection layer. The organic electroluminescent device according to any one of claims 1 to 4, the layer containing the interlock type compound characterized in that it is a light-emitting layer. 6. The organic electroluminescent element according to claim 4, wherein the thickness of the hole injection layer is 5 nm or more and 500 nm or less. The thickness of the said light emitting layer is 20 to 80 nm, The organic electroluminescent element of Claim 5 or Claim 6 characterized by the above-mentioned.