JP5724588B2 - ORGANIC ELECTROLUMINESCENT ELEMENT MATERIAL, ORGANIC ELECTROLUMINESCENT ELEMENT, DISPLAY DEVICE AND LIGHTING DEVICE - Google Patents

Description

  The present invention mainly relates to an organic electroluminescence element material, and also relates to an organic electroluminescence element, a display device, and an illumination device using the material.

Conventionally, as a light-emitting electronic display device, there is an electroluminescence display (hereinafter referred to as ELD). Examples of the constituent elements of ELD include inorganic electroluminescent elements and organic electroluminescent elements (hereinafter also referred to as organic EL elements).
Inorganic electroluminescent elements have been used as planar light sources, but an alternating high voltage is required to drive the light emitting elements.
On the other hand, an organic EL device has a structure in which a light-emitting layer containing a light-emitting compound is sandwiched between a cathode and an anode, and excitons (excitons) are generated by injecting electrons and holes into the light-emitting layer and recombining them. The device emits light by utilizing light emission (fluorescence / phosphorescence) when the exciton is deactivated. Since the organic EL element can emit light at a voltage of several V to several tens V, and is a self-luminous type, the viewing angle is wide, the visibility is high, and it is a thin film type completely solid element It attracts attention from the viewpoint of space saving and portability.

In the organic EL element, it is desired to develop an organic EL element that emits light efficiently and with high luminance with low power consumption for future practical use.
Specifically, a small amount of phosphor is doped into a stilbene derivative, a distyrylarylene derivative or a tristyrylarylene derivative to improve emission luminance, extend the lifetime of the device, and use an 8-hydroxyquinoline aluminum complex as a host compound. A device having an organic light emitting layer doped with a trace amount of a phosphor, a device having an organic light emitting layer doped with a quinacridone dye and a 8-hydroxyquinoline aluminum complex as a host compound are known.

However, when light emission from excited singlet is used as described above, the generation ratio of singlet excitons and triplet excitons is 1: 3, so the generation probability of luminescent excited species is 25%. Since the extraction efficiency is about 20%, the limit of the external extraction quantum efficiency (η) is set to 5%.
On the other hand, when the triplet is used, the upper limit of the internal quantum efficiency is 100%, so in principle the emission efficiency (external extraction quantum efficiency) is four times that of the excited singlet, which is almost equivalent to a cold cathode tube. It is attracting attention as a lighting application because there is a possibility that the above performance can be obtained.
For example, a heavy metal complex such as an iridium complex, tris (2-phenylpyridine) iridium as a dopant, L2Ir (acac) as a dopant, for example, (ppy) 2Ir (acac), and tris (2- (p-tolyl) pyridine) as a dopant Excited triplets using iridium (Ir (ptpy) 3), tris (benzo [h] quinoline) iridium (Ir (bzq) 3), etc. have been studied (these metal complexes are generally orthometalated iridium). Called complex).
In any case, the light emission luminance and the light emission efficiency in the case of a light emitting element are greatly improved as compared with conventional elements because the emitted light is derived from phosphorescence.
As host compounds of these phosphorescent dopants, carbazoles represented by 4,4′-bis (9-carbazolyl) biphenyl (CBP) and 1,3-bis (carbazol-9-yl) benzene (m-CP) Derivatives are well known.
However, m-CP and derivatives thereof are known as blue light-emitting host compounds, but the efficiency and life are not fully satisfied (for example, Patent Documents 1 and 2).

On the other hand, compounds having an indolocarbazole skeleton and the like are known as polycyclic compounds (for example, Patent Document 3). By using these, high efficiency and durability can be achieved to some extent, but further improvements have been demanded.
Compounds having a phenoxazine derivative condensed (for example, Patent Documents 4 and 5), compounds having a polycyclic structure containing P and Si (for example, Patent Documents 6 and 7), and a phenylcarbazole skeleton further condensed Compounds are also known (for example, Patent Documents 8 and 9). However, there is no description that the performance of the organic EL device is improved by further condensing these compounds.
A compound having a structure in which two carbazoles are condensed is also known (for example, Non-Patent Document 1), but an example in which these compounds are applied to an organic EL device is not known.

International Publication No. 03/80760 International Publication No. 04/74399 International Publication No. 07/063796 International Publication No. 07/031165 International Publication No. 10/050778 Special table 2008-545630 gazette JP 2003-243178 A US Pat. No. 7,842,405 International Publication No. 08/066357

Journal of the Chemical Society, 4492-4494 (1958)

As described above, in the present situation, the use of any compound has not sufficiently improved the originally required function of the organic EL element.
Therefore, the main object of the present invention is to improve the function originally required for the element itself, such as high luminous efficiency, long luminous lifetime, low driving voltage and small voltage increase during driving. It is to provide an organic electroluminescence element material, and also to provide an organic electroluminescence element, an illumination device, and a display device using the material.

In order to solve the above problems, according to the present invention,
An organic electroluminescence device material characterized by containing a compound represented by the general formula (1) or the general formula (2) is provided.

In formula (1), “X ₁ ” and “Y ₁ ” each independently represent any of N, P, P═O, P═S, SiAr ₁ , and “Z ₁ ” is a simple bond or NAr ₂ , O, S, PAr ₃ , P (═O) Ar ₄ , P (═S) Ar ₅ , or SiAr ₆ Ar ₇ .
“Ar _{1 to} Ar ₇ ” represents an aromatic hydrocarbon group or an aromatic heterocyclic group.
“A _{1 to} A ₁₄ ” each independently represent C—R _x1 or N, and the plurality of R _x1 may be the same or different.
“R _x1 ” each independently represents a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an alkoxyl group, a cycloalkoxyl group, Aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, amide group, carbamoyl group, sulfinyl group, alkylsulfonyl group or arylsulfonyl Group, amino group, nitro group, cyano group, hydroxyl group, alkylsilyl group or arylsilyl group, alkylphosphino group or arylphosphino group, alkylphosphoryl group or arylphosphoryl group, alkylthiophosphoryl group or aryl group Is any group selected from Ruchiohosuhoriru group.

In the formula (2), “X ₂ ” and “Y ₂ ” each independently represent a group having the same meaning as X ₁ and Y ₁ in the general formula (1), and “Z ₂ ” in the general formula (1) A group having the same meaning as Z ₁ is represented.
“A _{15 to} A ₂₈ ” each independently represent C—R _x2 or N, and the plurality of R _x2 may be the same or different.
“R _x2 ” each independently represents a group having the same _meaning as R _x1 in formula (1).

  According to the present invention, it is possible to improve the function originally required for the element itself, which has high light emission efficiency, long light emission life, low driving voltage, and small voltage increase during driving.

It is the schematic diagram which showed an example of the display apparatus comprised from an organic EL element. It is a schematic diagram of the display part of the display apparatus of FIG.

  Hereinafter, the best mode for carrying out the present invention will be described in detail, but the present invention is not limited thereto.

<< Organic EL element material (Organic electroluminescence element material) >>
The organic EL element material of the present invention will be described.
The organic EL device material of the present invention is characterized mainly by containing a compound represented by the general formula (1) or the general formula (2).

The organic EL device material of the present invention is preferably used for the light emitting layer of the organic EL device of the present invention, and particularly preferably used as a host compound in the light emitting layer.
The constituent layers and host compounds of the organic EL device of the present invention will be described in detail later.

By using a compound having a polycyclic condensed ring structure represented by the general formula (1) or the general formula (2) of the present invention, both high luminous efficiency and high durability (long life) can be achieved. all right.
A compound having a carbazole skeleton has been used as an electron transport material or a host material, but its efficiency and durability have been problems. Many polycyclic compounds that have been condensed to improve durability have been proposed so far, and although high efficiency and durability have been achieved to some extent, they have been practically used. Was still inadequate.
As a result of intensive studies in view of the above problems, the present inventors use a compound having a structure in which a polycyclic compound is further condensed, represented by the general formula (1) or the general formula (2) of the present invention. Thus, it was found that both high luminous efficiency and high durability (long life) can be achieved.
Such an effect is manifested because the organic EL material of the present invention has a more rigid condensed ring structure as represented by the general formula (1) or the general formula (2). . Thereby, the stability with respect to electric charge was improved, and a compound having excellent durability could be obtained. Furthermore, by containing heteroatoms such as N and P, strong charge transportability was exhibited, the voltage increase during driving was small at a low voltage, and higher luminous efficiency could be realized. As described above, by including heteroatoms such as N and P, the charge transport performance can be adjusted, the optimum charge transport property of electrons and holes can be exhibited, and as a hole transport material or an electron transport material Could be used. In particular, when used in the light-emitting layer, exciton generation and energy transfer to the dopant occur efficiently, so that recombination occurs efficiently and deterioration of the organic EL material can be prevented. As a result, not only high efficiency and low voltage but also high durability can be achieved, and further, voltage increase during driving can be suppressed to a small level.

<< Compound Represented by Formula (1) >>
The compound represented by the general formula (1) according to the present invention will be described.
In the general formula (1), “X ₁ ” and “Y ₁ ” each independently represent any _one of N, P, P═O, P═S, SiAr ₁ , and “Z ₁ ” is a simple bond or NAr _2. , O, S, PAr ₃ , P (═O) Ar ₄ , P (═S) Ar ₅ , or SiAr ₆ Ar ₇ .
“Ar _{1 to} Ar ₇ ” each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group, and particularly preferably an aromatic hydrocarbon group.

As a preferable form of “X ₁ ” and “Y ₁ ”, when either X ₁ or Y ₁ is N, the charge transport property / injection property of holes is further improved, which is preferable. Further, when either X ₁ or Y ₁ is P, P = O, or P = S, it is preferable because the electron charge transporting / injecting properties are further improved, and further, P = O or P = S is preferable, and P = O is particularly preferable.
On the other hand, when either X ₁ or Y ₁ is SiAr ₁ , the durability against electric charges is further improved, so that it is mentioned as one of particularly preferable embodiments. In particular, when X ₁ is N and Y ₁ is P = O, it is preferable because the charge transport properties of both holes and electrons can be improved. Further, X ₁ is N and Y ₁ is Si. In some cases, it has a charge transporting property of both holes and electrons, and the durability is improved.

As a preferable form of “Z ₁ ”, when Z ₁ is NAr ₂ , the charge transporting property / injecting property of holes is further improved, and PAr ₃ , P (═O) Ar ₄ , P (= S) Ar ₅ is preferred because the charge transporting / injecting property of electrons is further improved, and in that case, P (═O) Ar ₄ is particularly preferred.
On the other hand, when Z ₁ is SiAr ₆ Ar ₇ , the durability against electric charges is further improved, and therefore, it is mentioned as one of preferable modes.
Furthermore, when Z ₁ is a mere bond, it exhibits a particularly strong charge transport property and improves durability, so that it is mentioned as the most preferable form.

“A _{1 to} A ₁₄ ” each independently represent C—R _x1 or N, and the plurality of R _x1 may be the same or different.
When any one or more of A _{1 to} A ₁₄ is N, it is preferable because charge transportability is improved and a voltage increase during driving can be suppressed at a low voltage, and any one of A _{5 to} A ₁₄ is particularly preferable. Is preferably N. Furthermore, it is preferable that any one of A _{9 to} A ₁₄ is N, and it is particularly preferable that any one of A _{11 to} A ₁₄ is N.
On the other hand, when A _{1 to} A ₁₄ are C—R _{x 1} , not only has the charge transport property, but also the durability can be further improved.

“R _x1 ” in the general formula (1) represents hydrogen or a substituent.
Examples of the substituent represented by R _x1 include an alkyl group (eg, methyl group, ethyl group, propyl group, isopropyl group, (t) butyl group, pentyl group, hexyl group, octyl group, dodecyl group, tridecyl group, tetradecyl group). Group, pentadecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), alkenyl group (eg, vinyl group, allyl group, etc.), alkynyl group (eg, propargyl group, etc.), aromatic hydrocarbon group ( Also referred to as aryl group, for example, phenyl group, p-chlorophenyl group, mesityl group, tolyl group, xylyl group, naphthyl group, anthryl group, azulenyl group, acenaphthenyl group, fluorenyl group, phenanthryl group, indenyl group, pyrenyl group, biphenylyl group Etc.), heterocyclic groups (eg, epoxy ring, aziridine ring, Iran ring, oxetane ring, azetidine ring, thietane ring, tetrahydrofuran ring, dioxolane ring, pyrrolidine ring, pyrazolidine ring, imidazolidine ring, oxazolidine ring, tetrahydrothiophene ring, sulfolane ring, thiazolidine ring, ε-caprolactone ring, ε-caprolactam ring Piperidine ring, hexahydropyridazine ring, hexahydropyrimidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, 1,3-dioxane ring, 1,4-dioxane ring, trioxane ring, tetrahydrothiopyran ring, thiomorpholine ring, Thiomorpholine-1, 1-dioxide ring, pyranose ring, diazabicyclo [2,2,2] -octane ring), aromatic heterocyclic group (pyridyl group, pyrimidinyl group, furyl group, pyrrolyl group, imidazolyl group, benzimidazolyl group) Ryl group, pyrazolyl group, pyrazinyl group, triazolyl group (for example, 1,2,4-triazol-1-yl group, 1,2,3-triazol-1-yl group, etc.), oxazolyl group, benzooxazolyl group , Thiazolyl group, isoxazolyl group, isothiazolyl group, furazanyl group, thienyl group, quinolyl group, benzofuryl group, dibenzofuryl group, benzothienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carbolinyl group, diazacarbazolyl group ( One of the carbon atoms constituting the carboline ring of the carbolinyl group is replaced with a nitrogen atom), a quinoxalinyl group, a pyridazinyl group, a triazinyl group, a quinazolinyl group, a phthalazinyl group, etc.), a halogen atom (for example, a chlorine atom, a bromine group) Atom, iodine atom, fluorine atom, etc.), alkoxy Group (for example, methoxy group, ethoxy group, propyloxy group, pentyloxy group, hexyloxy group, octyloxy group, dodecyloxy group, etc.), cycloalkoxyl group (for example, cyclopentyloxy group, cyclohexyloxy group, etc.), aryl An oxy group (for example, phenoxy group, naphthyloxy group, etc.), an alkylthio group (for example, methylthio group, ethylthio group, propylthio group, pentylthio group, hexylthio group, octylthio group, dodecylthio group, etc.), a cycloalkylthio group (for example, cyclopentylthio group) Group, cyclohexylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkoxycarbonyl group (eg, methyloxycarbonyl group, ethyloxycarbonyl group, butyloxycarbonyl group, octyl group) Ruoxycarbonyl group, dodecyloxycarbonyl group, etc.), aryloxycarbonyl group (eg, phenyloxycarbonyl group, naphthyloxycarbonyl group, etc.), sulfamoyl group (eg, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, Butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), ureido group (for example, methylureido) Group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group , 2-pyridylaminoureido group, etc.), acyl group (for example, acetyl group, ethylcarbonyl group, propylcarbonyl group, pentylcarbonyl group, cyclohexylcarbonyl group, octylcarbonyl group, 2-ethylhexylcarbonyl group, dodecylcarbonyl group, phenylcarbonyl group) , Naphthylcarbonyl group, pyridylcarbonyl group, etc.), acyloxy group (eg, acetyloxy group, ethylcarbonyloxy group, butylcarbonyloxy group, octylcarbonyloxy group, dodecylcarbonyloxy group, phenylcarbonyloxy group, etc.), amide group ( For example, methylcarbonylamino group, ethylcarbonylamino group, dimethylcarbonylamino group, propylcarbonylamino group, pentylcarbonylamino group, cyclohexylcarbonylamino group. Group, 2-ethylhexylcarbonylamino group, octylcarbonylamino group, dodecylcarbonylamino group, phenylcarbonylamino group, naphthylcarbonylamino group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group) Propylaminocarbonyl group, pentylaminocarbonyl group, cyclohexylaminocarbonyl group, octylaminocarbonyl group, 2-ethylhexylaminocarbonyl group, dodecylaminocarbonyl group, phenylaminocarbonyl group, naphthylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.) Sulfinyl group (for example, methylsulfinyl group, ethylsulfinyl group, butylsulfinyl group, cyclohexylsulfinyl group, 2-ethyl Xylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, naphthylsulfinyl group, 2-pyridylsulfinyl group, etc.), alkylsulfonyl group or arylsulfonyl group (for example, methylsulfonyl group, ethylsulfonyl group, butylsulfonyl group, cyclohexylsulfonyl group, 2-ethylhexylsulfonyl group, dodecylsulfonyl group, phenylsulfonyl group, naphthylsulfonyl group, 2-pyridylsulfonyl group, etc.), amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, anilino group, diphenylamino group, naphthylamino group, 2-pyridylamino group, etc.), nitro group, cyano group, hydroxyl group, alkyl group Ryl group or arylsilyl group (for example, trimethylsilyl group, triethylsilyl group, (t) butyldimethylsilyl group, triisopropylsilyl group, (t) butyldiphenylsilyl group, triphenylsilyl group, trinaphthylsilyl group, 2-pyridyl Silyl group, etc.), alkylphosphino group or arylphosphino group (dimethylphosphino group, diethylphosphino group, dicyclohexylphosphino group, methylphenylphosphino group, diphenylphosphino group, dinaphthylphosphino group, di (2 -Pyridyl) phosphosphino group), alkyl phosphoryl group or aryl phosphoryl group (dimethylphosphoryl group, diethylphosphoryl group, dicyclohexylphosphoryl group, methylphenylphosphoryl group, diphenylphosphoryl group, dinaphthylphosphoryl group, di 2-pyridyl) phosphoryl group), alkylthiophosphoryl group or arylthiophosphoryl group (dimethylthiophosphoryl group, diethylthiophosphoryl group, dicyclohexylthiophosphoryl group, methylphenylthiophosphoryl group, diphenylthiophosphoryl group, dinaphthylthiophosphoryl group, di (2-pyridyl) thiophosphoryl group) and the like.
These substituents may be further substituted by the above substituents, or they may be condensed with each other to form a ring.

R _x1 is preferably an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, or a diarylamino group, and particularly preferably a substituent containing a nitrogen atom.
As the substituent containing a nitrogen atom, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group, a diarylamino group and the like are preferable, and a carbazolyl group or a carbolinyl group is particularly preferable.
If R _x1 represents a _substituent, preferably one of A 5 _{to A 14} is a _{C-R x1} is preferably Among them either _A 9 _{to A 14} is _{C-R x1,} particularly A _A preferred embodiment is that ₁₂ is C—R _x1 .

<< Compound Represented by Formula (2) >>
The compound represented by the general formula (2) according to the present invention will be described.
In the general formula (2), “X ₂ ” and “Y ₂ ” each independently represent any of N, P, P═O, P═S, SiAr ₉ , and “Z ₂ ” is a mere bond or NAr ₁₀ , O, S, PAr ₁₁ , P (═O) Ar ₁₂ , P (═S) Ar ₁₃ , or SiAr ₁₄ Ar ₁₅ .
“Ar _{9 to} Ar ₁₅ ” each independently represent a group having the same meaning as Ar _{1 to} Ar ₈ in the general formula (1), and an aromatic hydrocarbon group is particularly preferred.

As a preferable form of “X ₂ ” and “Y ₂ ”, when either X ₂ or Y ₂ is N, the charge transport property / injection property of holes is further improved, which is preferable. Further, when either X ₂ or Y ₂ is P, P = O, or P = S, it is preferable because the charge transport property / injection property of electrons is further improved, and further, P = O or P = S is preferable, and P = O is particularly preferable.
On the other hand, when either X ₂ or Y ₂ is SiAr ₉ , durability against electric charges is further improved, so that it is mentioned as one of particularly preferable embodiments. In particular, when X ₂ is N and Y ₂ is P═O, both the hole and electron charge transport properties can be improved, and X ₂ is N and Y ₂ is Si. In some cases, it has a charge transporting property of both holes and electrons, and the durability is improved.

As a preferable form of “Z ₂ ”, when Z ₂ is NAr ₁₀ , the charge transporting / injecting property of holes is further improved. PAr ₁₁ , P (═O) Ar ₁₂ , P (= S) Ar ₁₃ is preferred because the charge transporting / injecting properties of electrons are further improved, and in that case, P (═O) Ar ₁₂ is particularly preferred.
On the other hand, when Z ₂ is SiAr ₁₄ Ar ₁₅ , the durability against electric charges is further improved, and therefore, it is mentioned as one of preferable modes.
Further, when Z ₂ is a single bond exerts a particularly strong charge transport, and to improve durability against the charge, it is mentioned as the most preferred form.

“A _{15 to} A ₂₈ ” each independently represent C—R _x2 or N, and the plurality of R _x2 may be the same or different.
When any one or more of A _{15 to} A ₂₈ is N, it is preferable because charge transportability is improved and a voltage increase during driving can be suppressed at a low voltage, and any of A _{18 to} A ₂₈ is particularly preferable. N is preferred. Furthermore, it is preferable that any one of A _{22 to} A ₂₈ is N, and it is particularly preferable that any one of A _{25 to} A ₂₈ is N.
On the other hand, when A _{15 to} A ₂₈ are C—R _x2, it is one of the most preferable embodiments because it not only has charge transportability but also can improve durability.

In the general formula (2), “R _x2 ” represents hydrogen or a substituent.
_Examples of the substituent represented by R _x2 include the same substituents as the substituent represented by R _x1 in the general formula (1).
Among them, as R _x2 , an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a diarylamino group are preferable substituents, and a substituent containing a nitrogen atom is particularly preferable. .
As the substituent containing a nitrogen atom, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group, a diarylamino group, and the like are preferable, and a carbazolyl group or a carbolinyl group is particularly preferable.
If R _x2 represent a _substituent, preferably one of A 18 _{to A 28} is _{C-R x2} is preferably Among them either _A 22 _{to A 28} is _{C-R x2,} particularly A It is mentioned as a preferable form that ₂₆ is C-R _x2 .

  A particularly preferred form of the above general formula (1) or general formula (2) is represented by the following general formula (3) or general formula (4).

<< Compound Represented by Formula (3) >>
The compound represented by the general formula (3) according to the present invention will be described.
In the general formula (3), “X ₃ ” and “Y ₃ ” each independently represent any of N, P, P═O, P═S, and SiAr ₈ .
“Ar ₈ ” independently represents a group having the same meaning as Ar _{1 to} Ar ₇ in Formula (1), and an aromatic hydrocarbon group is particularly preferable.

As a preferable form of “X ₃ ” and “Y ₃ ”, when either X ₃ or Y ₃ is N, it is preferable because the charge transport property / injection property of holes is further improved. In addition, when either X ₃ or Y ₃ is P, P = O, or P = S, it is preferable because the charge transport property / injection property of electrons is further improved. Further, P = O or P = S is preferable, and P = O is particularly preferable.
On the other hand, when either X ₃ or Y ₃ is SiAr ₈ , the durability against electric charges is further improved, so that it is mentioned as one of particularly preferable embodiments. In particular, when X ₃ is N and Y ₃ is P = O, it is preferable because the charge transportability of both holes and electrons can be improved. Further, X ₃ is N and Y ₃ is Si. In some cases, it has a charge transporting property of both holes and electrons, and the durability is improved.

“A _{29 to} A ₄₂ ” each independently represent C—R _x3 or N, and the plurality of R _x3 may be the same or different.
When any one or more of A _{29 to} A ₄₂ is N, it is preferable because charge transportability is improved and a voltage increase during driving can be suppressed at a low voltage, and any one of A _{33 to} A ₄₂ is particularly preferable. N is preferred. Furthermore, any one of A _{37 to} A ₄₂ is preferably N, and it is particularly preferable that any one of A _{39 to} A ₄₂ is N.
On the other hand, when A _{29 to} A ₄₂ are C—R _x3, it is one of the most preferable embodiments because it not only has charge transport properties but also can improve durability.

In the general formula (3), “R _X3 ” represents hydrogen or a substituent.
_Examples of the substituent represented by R _X3 include the same substituents as the substituent represented by R _X1 in the general formula (1).
Among them, as R _X3 , an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a diarylamino group are preferable substituents, and a substituent containing a nitrogen atom is particularly preferable. .
As the substituent containing a nitrogen atom, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group, a diarylamino group, and the like are preferable, and a carbazolyl group or a carbolinyl group is particularly preferable.
If R _x3 represents a _substituent, preferably one of A 33 _{to A 42} is _{C-R x3} is preferably Among them either _A 37 _{to A 42} is _{C-R x3,} especially A ₄₀ is preferably C—R _x3 .

<< Compound Represented by Formula (4) >>
The compound represented by the general formula (4) according to the present invention will be described.
In the general formula (4), “X ₄ ” and “Y ₄ ” each independently represent N, P, P═O, P═S, or SiAr ₁₆ .
“Ar ₁₆ ” independently represents a group having the same meaning as Ar _{1 to} Ar ₈ in Formula (1), and an aromatic hydrocarbon group is particularly preferable.

As a preferable form of “X ₄ ” and “Y ₄ ”, when either X ₄ or Y ₄ is N, it is preferable because the charge transport property / injection property of holes is further improved. Further, when either X ₄ or Y ₄ is P, P = O, or P = S, it is preferable because the charge transport property / injection property of electrons is further improved, and further, P = O or P = S is preferable, and P = O is particularly preferable.
On the other hand, when either X ₄ or Y ₄ is SiAr ₁₆ , the durability against electric charges is further improved, so that it is mentioned as one of particularly preferable embodiments. In particular, when X ₄ is N and Y ₄ is P = O, it is preferable because the charge transportability of both holes and electrons can be improved. Further, X ₄ is N and Y ₄ is Si. In some cases, it has a charge transporting property of both holes and electrons, and the durability is improved.

“A _{29 to} A ₄₂ ” each independently represent C—R _x4 or N, and the plurality of R _x4 may be the same or different.
When any one or more of A _{43 to} A ₅₆ is N, it is preferable because charge transportability is improved and a voltage increase during driving can be suppressed at a low voltage, and any of A _{46 to} A ₅₆ is particularly preferable. N is preferred. Furthermore, it is preferable that any one of A _{50 to} A ₅₆ is N, and it is particularly preferable that any one of A _{53 to} A ₅₆ is N.
On the other hand, when A _{43 to} A ₄₆ are C—R _x4, it is one of the most preferable modes because it not only has charge transport properties but also can improve durability.

“R _x4 ” in the general formula (4) represents hydrogen or a substituent.
_Examples of the substituent represented by R _x4 include the same substituents as the substituent represented by R _x1 in the general formula (1).
Among them, as R _x4 , an arylsilyl group, an arylphosphoryl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a diarylamino group are preferable substituents, and a substituent containing a nitrogen atom is particularly preferable. .
As the substituent containing a nitrogen atom, a carbazolyl group, a carbolinyl group, a diazacarbazolyl group, a diarylamino group, and the like are preferable, and a carbazolyl group or a carbolinyl group is particularly preferable.
If R _x3 represents a _substituent, preferably one of A 46 _{to A 56} is _{C-R x4} is preferably Among them either _A 50 _{to A 56} is _{C-R x4,} especially A _A preferred form is that ₅₄ is C—R _x4 .

  Specific examples of the compound according to the present invention are shown below, but the present invention is not limited thereto.

  Hereinafter, although an example of the synthesis | combination of the compound represented by General formula (1) or General formula (2) based on this invention is shown, this invention is not limited to these.

<< Synthesis Example; Synthesis of Exemplified Compound 2-107 >>

(1) Synthesis of Intermediate 1 2-aminobiphenyl 10.0 g (50 mmol), 2-nitrobiphenyl 8.5 g (50 mmol) and potassium hydroxide 8.4 g (150 mmol) were added to 80 ml of toluene, and the mixture was heated to reflux for 24 hours. went. After the reaction solution was cooled to room temperature, the precipitated solid was collected by filtration and dried. The obtained solid was recrystallized from dichloromethane to obtain 3.5 g (yield 20%) of Intermediate 1 as a yellow solid. The structure of Intermediate 1 was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(2) Synthesis of Exemplary Compound 2-107 3.5 g (10 mmol) of Intermediate 1 and 10% palladium / carbon 5 g were stirred and heated at 350 ° C. for 6 hours under a hydrogen stream. After cooling the reaction solution to room temperature, the solid was filtered off, water was added, and the mixture was extracted with dichloromethane. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The obtained solid was recrystallized from xylene to obtain 1.85 g (yield 56%) of Exemplary Compound 2-107 as a yellow solid. The structure was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

<< Synthesis Example; Synthesis of Exemplary Compound 1-106 and Exemplary Compound 2-107 >>

(1) Synthesis of Intermediate 2 In the above, intermediate 2 is, for example, Chem. Ber. 127 (1994), pages 1723 to 1728, and the like.

(2) Synthesis of Intermediate 3 9.1 g (50 mmol) of Intermediate 2, 1,2-dibromobenzene 70 g (300 mmol), copper powder 5 g, potassium carbonate 27.6 g (200 mmol) were added at 200 ° C. under a nitrogen stream at 12 ° C. Heated for hours. The reaction mixture was cooled to room temperature, copper was filtered off, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 16.7 g of intermediate 3 (yield 68%). The structure of Intermediate 3 was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(3) Synthesis of Exemplified Compound 1-106 and Exemplified Compound 2-107 Under a nitrogen stream, 16.7 g (34 mmol) of Intermediate 3, 1.5 g (6.8 mmol) of palladium acetate, 5 g of tricyclohexylphosphonium tetrafluoroborate (13.6 mmol), 18.8 g (136 mmol) of potassium carbonate, and 170 ml of dimethylacetamide were added, and heating reflux was performed for 6 minutes. After cooling the reaction solution to room temperature, the solid was filtered off, water was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 2.9 g (yield 26%) of exemplary compound 1-106 and 3.8 g (yield 34%) of exemplary compound 2-107. The structures of Exemplified Compound 1-106 and Exemplified Compound 2-107 were confirmed by nuclear magnetic resonance spectrum and mass spectrum.

<< Synthesis Example; Synthesis of Exemplary Compound 1-122 and Exemplary Compound 2-113 >>

(1) Synthesis of Intermediate 4 Under a nitrogen stream, 2.0 g (9 mmol) of palladium acetate and 15 ml of a 50% xylene solution of tributylphosphine were added and stirred at room temperature for 30 minutes. Subsequently, 300 ml of dehydrated xylene, 42.5 g (180 mmol) of 1,2-dibromobenzene, 9.6 g (90 mmol) of benzylamine, and 25.9 g (270 mmol) of sodium t-butylate were added, and the mixture was heated under reflux for 7 minutes. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 24.8 g of Intermediate 4 (yield 66%). The structure was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(2) Synthesis of Intermediate 5 Under a nitrogen stream, 24 g (100 mmol) of 1,2-dibromobenzene, 2.4 g (100 mmol) of magnesium and 200 ml of tetrahydrofuran were added and stirred for 1 hour. After the reaction solution was cooled to 0 ° C., 100 ml of a tetrahydrofuran solution of 21 g (100 mmol) of trichlorophenylsilane was slowly added dropwise. The reaction solution was returned to room temperature and stirred for 3 hours. The solid was filtered off under nitrogen and the filtrate was concentrated under reduced pressure. The obtained crude product 19.9 g (yield 60%) was used for the next reaction without further purification.

(3) Synthesis of Intermediate 6 After cooling 200 ml of a tetrahydrofuran solution of 24.8 g of Intermediate 4 (60 mmol) to 0 ° C. under a nitrogen stream, 76 ml of a hexane solution (1.65 mol / L) of n-butyllithium was added. The solution was slowly added dropwise and stirred for 1 hour. 100 ml of a tetrahydrofuran solution of 19.9 g of intermediate 5 (60 mmol) was slowly added dropwise to the reaction solution. After returning the reaction solution to room temperature, heating reflux was performed for 4 hours. The reaction solution was returned to room temperature, water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 19.0 g of intermediate 6 (yield 61%). The structure was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(4) Synthesis of Intermediate 7 Under a nitrogen stream, 19.0 g (37 mmol) of Intermediate 6, 0.83 g (3.7 mmol) of palladium acetate, 2.7 g (7.4 mmol) of tricyclohexylphosphonium tetrafluoroborate, Potassium carbonate (10.2 g, 74 mmol) and dimethylacetamide (120 ml) were added, and the mixture was heated to reflux for 7 hours. After cooling the reaction solution to room temperature, the solid was filtered off, water was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 12.0 g (yield 75%) of Intermediate 7. The structure of Intermediate 7 was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(5) Synthesis of Intermediate 8 To 12.0 g (27 mmol) of Intermediate 7 and 10% palladium / carbon 5 g were added 150 ml of dichloromethane and 150 ml of acetic acid, and the mixture was stirred under a hydrogen stream for 6 hours. The solid was filtered off and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 6.8 g of intermediate 8 (yield 72%). The structure of intermediate 8 was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(6) Synthesis of intermediate 9 6.8 g (19 mmol) of intermediate 8, 1,2-dibromobenzene 26.9 g (114 mmol), copper powder 1.8 g, potassium carbonate 5.2 g (38 mmol) under nitrogen stream Heated at 200 ° C. for 12 hours. The reaction mixture was cooled to room temperature, copper was filtered off, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 6.2 g of intermediate 9 (yield 65%). The structure of the intermediate 9 was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(7) Synthesis of Exemplified Compound 1-122 and Exemplified Compound 2-113 Under a nitrogen stream, 6.2 g (12 mmol) of Intermediate 9, 0.27 g (1.2 mmol) of palladium acetate, tricyclohexylphosphonium tetrafluoroborate 0 .88 g (2.4 mmol), potassium carbonate 3.3 g (24 mmol) and dimethylacetamide 120 ml were added, and the mixture was heated and refluxed for 7 minutes. After cooling the reaction solution to room temperature, the solid was filtered off, water was added to the filtrate, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 1.2 g (yield 23%) of exemplary compound 1-122 and 1.92 g (38% yield) of exemplary compound 2-113. The structures of Exemplified Compound 1-122 and Exemplified Compound 2-113 were confirmed by nuclear magnetic resonance spectrum and mass spectrum.

<< Synthesis Example; Synthesis of Exemplary Compound 1-126 >>

(1) Synthesis of Intermediate 10 0.50 g (2.8 mmol) of N-bromosuccinimide was added to 28 ml of a dichloromethane solution of 1.2 g (2.8 mmol) of Exemplified Compound 1-122 and diffused at room temperature for 6 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 1.0 g of intermediate 10 (yield 74%). The structure was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(2) Synthesis of Exemplified Compound 1-126 Under a nitrogen stream, 90 mg (0.40 mmol) of palladium acetate and 0.6 ml of a 50% xylene solution of tributylphosphine were added and stirred at room temperature for 30 minutes. Subsequently, 7 ml of dehydrated xylene, 1.0 g (2.0 mmol) of Intermediate 10, 350 mg (2.1 mmol) of carbazole and 0.58 g (6.0 mmol) of sodium t-butylate were added, and the mixture was refluxed for 7 minutes. . The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 1.0 g (yield 88%) of Exemplary Compound 1-126. The structure was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

<< Synthesis Example; Synthesis of Exemplary Compound 2-74 >>

(1) Synthesis of Intermediate 11 Under a nitrogen stream, 330 ml of a tetrahydrofuran solution of 39 g (100 mmol) of 2,2 ′, 5-tribromobiphenyl was cooled to −78 ° C., and then a hexane solution of n-butyllithium (1.65 mol). / L) 122 ml was slowly added dropwise and stirred for 1 hour. 8.7 ml (100 mmol) of this reaction solution phosphorus trichloride was slowly added dropwise. After returning the reaction solution to room temperature, heating reflux was performed for 1 hour. The solid was filtered off under nitrogen and the filtrate was concentrated under reduced pressure. The obtained crude product (15.2 g, yield 51%) was used for the next reaction without further purification.

(2) Synthesis of Intermediate 12 Under a nitrogen stream, 14 g (51 mmol) of 1,3-dibromo-2-nitrobenzene, 1.2 g (51 mmol) of magnesium and 100 ml of tetrahydrofuran were added and stirred for 1 hour. The reaction solution was cooled to 0 ° C., and then 70 ml of a tetrahydrofuran solution containing 15.2 g (51 mmol) of the intermediate 11 was slowly added dropwise. The reaction solution was returned to room temperature and stirred for 3 hours. Water was added to the reaction solution, the solid was filtered off, and the filtrate was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 11.6 g (yield 49%) of a solid.
80 ml of an ethyl acetate solution of 11.6 g (25 mmol) of the solid obtained above was cooled to 0 ° C., and 10 ml of 35% aqueous hydrogen peroxide was slowly added dropwise. The reaction solution was returned to room temperature and concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 10.8 g of intermediate 12 (yield 90%). The structure was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(3) Synthesis of Intermediate 13 Under a nitrogen stream, 0.52 g (2.3 mmol) of palladium acetate and 4.3 ml of 50% xylene solution of tributylphosphine were added and stirred at room temperature for 30 minutes. Subsequently, 80 ml of dehydrated xylene, 10.8 g (23 mmol) of intermediate 12, 5.7 g (23 mmol) of 2-bromophenylaniline, and 6.6 g (69 mmol) of sodium t-butylate were added, and the mixture was heated to reflux for 7 hours. . The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 4.6 g of intermediate 13 (yield 31%). The structure was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(4) Synthesis of Intermediate 14 To 4.6 g (7.1 mmol) of Intermediate 13, 10% palladium / carbon 2 g, 75 ml of ethanol was added and stirred for 6 hours under a hydrogen stream. The solid was filtered off and the filtrate was concentrated under reduced pressure. The obtained crude product was purified by silica gel column chromatography to obtain 3.9 g of intermediate 14 (yield 89%). The structure of intermediate 8 was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

(5) Synthesis of Exemplary Compound 2-74 Under a nitrogen stream, 282 mg (1.3 mmol) of palladium acetate and 6 ml of a 50% xylene solution of tributylphosphine were added and stirred at room temperature for 30 minutes. Subsequently, 63 ml of dehydrated xylene, 3.9 g (6.3 mmol) of the intermediate 14 and 3.6 g (38 mmol) of sodium t-butyrate were added, and heated to reflux for 6 hours. The reaction mixture was cooled to room temperature, water was added, and the mixture was extracted with ethyl acetate. The organic layer was repeatedly washed with water and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography to obtain 1.46 g (yield 51%) of Exemplary Compound 2-74. The structure was confirmed by nuclear magnetic resonance spectrum and mass spectrum.

<< Constituent layers of organic EL elements >>
The constituent layers of the organic EL element of the present invention will be described.
In this invention, although the preferable specific example of the layer structure of an organic EL element is shown below, this invention is not limited to these.
(I) Anode / light emitting layer / electron transport layer / cathode (ii) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (iii) anode / hole transport layer / light emitting layer / hole blocking layer / electron Transport layer / cathode (iv) anode / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / cathode buffer layer / cathode (v) anode / anode buffer layer / hole transport layer / light emitting layer / hole Blocking layer / electron transport layer / cathode buffer layer / cathode

In the present invention, the compound represented by the general formula (1) or the general formula (2) may be contained in any layer of the organic EL element. It is preferably contained in one or more layers, and more preferably contained in the light emitting layer or the electron transport layer.
Furthermore, the compound represented by the general formula (1) or the general formula (2) is more preferably contained in the light emitting layer, and most preferably contained as a host compound in the light emitting layer.

In the organic EL device of the present invention, the blue light emitting layer preferably has an emission maximum wavelength of 430 to 480 nm, the green light emitting layer has an emission maximum wavelength of 510 to 550 nm, and the red light emitting layer has an emission maximum wavelength of 600 to 640 nm. A monochromatic light emitting layer in the range is preferable, and a display device using these is preferable.
Alternatively, a white light emitting layer may be formed by laminating at least three light emitting layers. Further, a non-light emitting intermediate layer may be provided between the light emitting layers. The organic EL element of the present invention preferably emits white light and is preferably a lighting device using these.

Each layer which comprises the organic EL element of this invention is demonstrated.
《Electron transport layer》
The electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
In the case of a single-layer electron transport layer and multiple layers, the electron transport material used for the electron transport layer adjacent to the cathode side with respect to the light-emitting layer has a function of transmitting electrons injected from the cathode to the light-emitting layer. As the material, the effect of the present invention can be achieved by using the electron transport material according to the present invention, but, in addition, in the range not impairing the effect of the electron transport material according to the present invention. Any one of known compounds can be selected and used in combination, for example, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone. Derivatives, oxadiazole derivatives and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be exemplified. Furthermore, the polymeric material which introduce | transduced these materials into the polymer chain, or made these materials into the polymeric principal chain can also be mentioned.
Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu Metal complexes in which Ca, Sn, Ga or Pb is replaced can also be mentioned. In addition, metal-free or metal phthalocyanine, or those having a terminal substituted with an alkyl group or a sulfonic acid group can also be mentioned. In addition, the distyrylpyrazine derivative can include inorganic semiconductors such as n-type-Si and n-type-SiC.

The electron transport layer can be formed by thinning the electron transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method.
Although there is no restriction | limiting in particular about the film thickness of an electron carrying layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm.
The electron transport layer may have a single layer structure composed of one or more of the above materials.
It can also be used as an electron transport layer having a high n property doped with impurities. Examples thereof include JP-A-4-297076, JP-A-10-270172, JP-A-2000-196140, 2001-102175, J.A. Appl. Phys. 95, 5773 (2004), and the like.
It is preferable to use such an n-type electron transport layer because an element with lower power consumption can be manufactured.

<Light emitting layer>
The light-emitting layer is a layer that emits light by recombination of electrons and holes injected from the electrode, the electron transport layer, or the hole transport layer, and the light-emitting portion is the light-emitting layer even in the layer of the light-emitting layer. It may be an interface with an adjacent layer.
The total film thickness of the light emitting layer is not particularly limited, but from the viewpoint of improving the uniformity of the film, preventing unnecessary application of high voltage during light emission, and improving the stability of the emission color with respect to the drive current. It is preferably adjusted to a range of 2 nm to 5 μm, more preferably adjusted to a range of 2 nm to 200 nm, and particularly preferably adjusted to a range of 10 nm to 80 nm.
For the production of the light-emitting layer, a host compound or a light-emitting dopant, which will be described later, is formed by forming a film by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, an LB method, or an inkjet method. it can.
The light emitting layer of the organic EL device of the present invention preferably contains a light emitting host compound and at least one kind of light emitting dopant (such as a phosphorescent dopant (also referred to as a phosphorescent dopant) or a fluorescent dopant).

(1) Host compound (also referred to as light-emitting host)
The light-emitting host compound used in the present invention is not particularly limited in terms of structure, but typically, a carbazole derivative, a triarylamine derivative, an aromatic borane derivative, a nitrogen-containing heterocyclic compound, a thiophene derivative, a furan derivative, Those having a basic skeleton, such as an oligoarylene compound, or a carboline derivative or a diazacarbazole derivative (herein, a diazacarbazole derivative means that at least one carbon atom of a hydrocarbon ring constituting a carboline ring of a carboline derivative is nitrogen Represents an atom substituted with an atom.) And the like.
In the present invention, the host compound has a mass ratio of 20% or more of the compound contained in the light emitting layer and a phosphorescence quantum yield of phosphorescence of less than 0.1 at room temperature (25 ° C.). Defined as a compound.
The host compound preferably has a phosphorescence quantum yield of less than 0.01.
The host compound preferably has a mass ratio in the layer of 20% or more among the compounds contained in the light emitting layer.

As the host compound, the above host compounds may be used alone or in combination of two or more. By using a plurality of types of host compounds, it is possible to adjust the movement of charges, and the organic EL element can be made highly efficient.
Moreover, it becomes possible to mix different light emission by using multiple types of the compound containing the partial structure represented by the said General formula (1), and the light emission dopant mentioned later, and can obtain arbitrary luminescent colors by this. it can.

The light emitting host used in the present invention may be a conventionally known low molecular compound or a high molecular compound having a repeating unit, and a low molecular compound having a polymerizable group such as a vinyl group or an epoxy group (deposition polymerization property). Light emitting host).
As a known host compound that may be used in combination, a compound that has a hole transporting ability and an electron transporting ability, prevents the emission of light from being increased in wavelength, and has a high Tg (glass transition temperature) is preferable.
Specific examples of known host compounds include compounds described in the following documents.
JP-A-2001-257076, 2002-308855, 2001-313179, 2002-319491, 2001-357777, 2002-334786, 2002-8860, 2002-334787, 2002-15871, 2002-334788, 2002-43056, 2002-334789, 2002-75645, 2002-338579, 2002-105445 gazette, 2002-343568 gazette, 2002-141173 gazette, 2002-352957 gazette, 2002-203683 gazette, 2002-363227 gazette, 2002-231453 gazette, No. 003-3165, No. 2002-234888, No. 2003-27048, No. 2002-255934, No. 2002-286061, No. 2002-280183, No. 2002-299060, No. 2002. -302516, 2002-305083, 2002-305084, 2002-308837, etc.

(2) Luminescent dopant A luminescent dopant is demonstrated.
As the light-emitting dopant, a phosphorescent dopant (also referred to as a phosphorescent emitter, a phosphorescent compound, a phosphorescent compound, or the like) or a fluorescent dopant (also referred to as a fluorescent compound) can be used.
From the viewpoint of obtaining an organic EL device with higher luminous efficiency, the light emitting dopant (sometimes referred to simply as the light emitting material) used in the light emitting layer or the light emitting unit of the organic EL device of the present invention is the above general formula ( It is preferable to contain the compound containing the partial structure represented by 1) as a phosphorescent dopant.

(2.1) Phosphorescent dopant The phosphorescent dopant according to the present invention will be described.
The phosphorescent dopant according to the present invention is a compound in which light emission from an excited triplet is observed. Specifically, the phosphorescent dopant is a compound that emits phosphorescence at room temperature (25 ° C.) and has a phosphorescence quantum yield of 25. Although it is defined as a compound of 0.01 or more at ° C., a preferable phosphorescence quantum yield is 0.1 or more.
The phosphorescence quantum yield can be measured by the method described in Spectroscopic II, page 398 (1992 edition, Maruzen) of Experimental Chemistry Course 4 of the 4th edition.
Although the phosphorescence quantum yield in a solution can be measured using various solvents, the phosphorescence dopant according to the present invention achieves the phosphorescence quantum yield (0.01 or more) in any solvent. That's fine.

There are two types of emission principles of the phosphorescent dopant.
One is that the recombination of carriers occurs on the host compound to which carriers are transported to generate an excited state of the host compound, and this energy is transferred to the phosphorescent dopant to obtain light emission from the phosphorescent dopant. The other is a carrier trap type in which the phosphorescent dopant becomes a carrier trap, and recombination of carriers occurs on the phosphorescent dopant to emit light from the phosphorescent dopant.
In any light emission principle, it is necessary that the excited state energy of the phosphorescent dopant is lower than the excited state energy of the host compound.

  The phosphorescent dopant according to the present invention is a phosphorescent metal complex, preferably a complex compound containing a group 8-10 metal in the periodic table, more preferably an iridium compound, an osmium compound, Alternatively, a platinum compound (platinum complex compound) or a rare earth complex, and most preferably an iridium compound.

In this invention, the well-known phosphorescence dopant used for the light emitting layer of an organic EL element can be used.
Although the specific example of the well-known compound used as a phosphorescence dopant below is shown, this invention is not limited to these. These compounds are described, for example, in Inorg. Chem. 40, 1704-1711, and the like.

(2.2) Fluorescent dopant (also called fluorescent compound)
Fluorescent dopants (fluorescent compounds) include coumarin dyes, pyran dyes, cyanine dyes, croconium dyes, squalium dyes, oxobenzanthracene dyes, fluorescein dyes, rhodamine dyes, pyrylium dyes, perylene dyes Examples thereof include dyes, stilbene dyes, polythiophene dyes, and rare earth complex phosphors.

Next, an injection layer, a blocking layer, an electron transport layer, and the like used as a constituent layer of the organic EL element of the present invention will be described.
<< Injection layer: electron injection layer, hole injection layer >>
An injection layer is provided as necessary, and there are an electron injection layer and a hole injection layer, and as described above, exists between the anode and the light emitting layer or the hole transport layer, and between the cathode and the light emitting layer or the electron transport layer. You may let them.
An injection layer is a layer provided between an electrode and an organic layer in order to reduce drive voltage and improve light emission luminance. “Organic EL element and its forefront of industrialization (issued by NTT Corporation on November 30, 1998) 2), Chapter 2, “Electrode Materials” (pages 123 to 166) in detail, and includes a hole injection layer (anode buffer layer) and an electron injection layer (cathode buffer layer).
The details of the anode buffer layer (hole injection layer) are described in JP-A-9-45479, JP-A-9-260062, JP-A-8-288069 and the like. As a specific example, copper phthalocyanine is used. Examples thereof include a phthalocyanine buffer layer represented by an oxide, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a polymer buffer layer using a conductive polymer such as polyaniline (emeraldine) or polythiophene.
The details of the cathode buffer layer (electron injection layer) are described in JP-A-6-325871, JP-A-9-17574, JP-A-10-74586, and the like. Specifically, strontium, aluminum, etc. Metal buffer layer typified by lithium, alkali metal compound buffer layer typified by lithium fluoride, alkaline earth metal compound buffer layer typified by magnesium fluoride, oxide buffer layer typified by aluminum oxide, etc. .
The buffer layer (injection layer) is preferably a very thin film, and the film thickness is preferably in the range of 0.1 nm to 5 μm although it depends on the material.

<Blocking layer: hole blocking layer, electron blocking layer>
The blocking layer is provided as necessary in addition to the basic constituent layer of the organic compound thin film as described above. For example, it is described in JP-A Nos. 11-204258, 11-204359, and “Organic EL elements and their forefront of industrialization” (issued by NTT, Inc. on November 30, 1998). There is a hole blocking (hole blocking) layer.
The hole blocking layer has a function of an electron transport layer in a broad sense, and is made of a hole blocking material that has a function of transporting electrons and has a remarkably small ability to transport holes. The probability of recombination of electrons and holes can be improved by blocking. Moreover, the structure of the electron carrying layer mentioned later can be used as a hole-blocking layer concerning this invention as needed.
The hole blocking layer of the organic EL device of the present invention is preferably provided adjacent to the light emitting layer.
The hole blocking layer preferably contains the carbazole derivative, carboline derivative or diazacarbazole derivative mentioned as the host compound.
Further, in the present invention, when a plurality of light emitting layers having different emission colors are provided, the light emitting layer whose emission maximum wavelength is the shortest is preferably closest to the anode among all the light emitting layers. In this case, it is preferable to additionally provide a hole blocking layer between the shortest wave layer and the light emitting layer next to the anode next to the anode. Furthermore, it is preferable that 50% by mass or more of the compound contained in the hole blocking layer provided at the position has an ionization potential of 0.3 eV or more larger than the host compound of the shortest wave emitting layer.

The ionization potential is defined by the energy required to emit an electron at the HOMO (highest occupied molecular orbital) level of the compound to the vacuum level, and can be obtained by the following method, for example.
(1) Using Gaussian 98 (Gaussian 98, Revision A.11.4, MJ Frisch, et al, Gaussian, Inc., Pittsburgh PA, 2002.), a molecular orbital calculation software manufactured by Gaussian, USA The ionization potential can be obtained as a value obtained by rounding off the second decimal place of the value (eV unit converted value) calculated by performing structural optimization using B3LYP / 6-31G *. This calculation value is effective because the correlation between the calculation value obtained by this method and the experimental value is high.
(2) The ionization potential can also be obtained by a method of directly measuring by photoelectron spectroscopy. For example, a method known as ultraviolet photoelectron spectroscopy can be suitably used by using a low energy electron spectrometer “Model AC-1” manufactured by Riken Keiki Co., Ltd.

On the other hand, the electron blocking layer has a function of a hole transport layer in a broad sense, and is made of a material that has a function of transporting holes and has an extremely small ability to transport electrons, and transports electrons while transporting holes. By blocking, the recombination probability of electrons and holes can be improved.
Moreover, the structure of the positive hole transport layer mentioned later can be used as an electron blocking layer as needed.
The film thickness of the hole blocking layer and the electron transport layer according to the present invention is preferably 3 to 100 nm, and more preferably 5 to 30 nm.

《Hole transport layer》
The hole transport layer is made of a hole transport material having a function of transporting holes, and in a broad sense, a hole injection layer and an electron blocking layer are also included in the hole transport layer.
The hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any of hole injection or transport and electron barrier properties, and may be either organic or inorganic. For example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, Examples thereof include stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers.

The above-mentioned materials can be used as the hole transport material, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
Representative examples of aromatic tertiary amine compounds and styrylamine compounds include N, N, N ', N'-tetraphenyl-4,4'-diaminophenyl; N, N'-diphenyl-N, N'- Bis (3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine (TPD); 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl; 1,1-bis (4-di-p-tolyl) Aminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N ' − (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4'-N, N-diphenylaminostilbenzene; N-phenylcarbazole, as well as two of those described in US Pat. No. 5,061,569 Having a condensed aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine in which three triphenylamine units described in Japanese Patent No. 88 are linked in a starburst type ( MTDATA) and the like.
Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used. In addition, inorganic compounds such as p-type-Si and p-type-SiC can also be used as the hole injection material and the hole transport material.
JP-A-11-251067, J. Org. Huang et al. A so-called p-type hole transport material as described in a book (Applied Physics Letters 80 (2002), p. 139) can also be used. In the present invention, these materials are preferably used because a light-emitting element with higher efficiency can be obtained.

The hole transport layer can be formed by thinning the hole transport material by a known method such as a vacuum deposition method, a spin coating method, a casting method, a printing method including an ink jet method, or an LB method. it can.
Although there is no restriction | limiting in particular about the film thickness of a positive hole transport layer, Usually, 5 nm-about 5 micrometers, Preferably it is 5-200 nm.
This hole transport layer may have a single layer structure composed of one or more of the above materials.
Alternatively, a hole transport layer having a high p property doped with impurities can be used. Examples thereof include JP-A-4-297076, JP-A-2000-196140, 2001-102175, J. Pat. Appl. Phys. 95, 5773 (2004), and the like.
In the present invention, it is preferable to use a hole transport layer having such a high p property because a device with lower power consumption can be produced.

"anode"
As the anode in the organic EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used.
Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used.
For the anode, these electrode materials may be formed into a thin film by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or when pattern accuracy is not so high (about 100 μm or more) A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. Or when using the substance which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used.
When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less.
Further, although the film thickness depends on the material, it is usually in the range of 10 to 1000 nm, preferably in the range of 10 to 200 nm.

"cathode"
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used.
Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function than this, for example, a magnesium / silver mixture, Magnesium / aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures, aluminum and the like are preferred.
The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm.
In order to transmit the emitted light, if either one of the anode or the cathode of the organic EL element is transparent or translucent, the emission luminance is advantageously improved.
Moreover, after producing the said metal with a film thickness of 1-20 nm on a cathode, the transparent or semi-transparent cathode can be produced by producing the electroconductive transparent material quoted by description of the anode on it, By applying this, an element in which both the anode and the cathode are transmissive can be manufactured.

《Support substrate》
As a support substrate (hereinafter also referred to as a substrate, substrate, substrate, support, etc.) that can be used in the organic EL device of the present invention, there is no particular limitation on the type of glass, plastic, etc., and it is transparent. May be opaque.

When extracting light from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include glass, quartz, and a transparent resin film. A particularly preferable support substrate is a resin film capable of giving flexibility to the organic EL element.
Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate propionate (CAP), Cellulose esters such as cellulose acetate phthalate (TAC) and cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, Cycloolefin resins such as polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylate, Arton (trade name, manufactured by JSR) or Appel (trade name, manufactured by Mitsui Chemicals) Can be mentioned.

An inorganic film, an organic film, or a hybrid film of both may be formed on the surface of the resin film, and the water vapor permeability (25 ± 0.5 ° C.) measured by a method according to JIS K 7129-1992. , Relative humidity (90 ± 2)% RH) is preferably 0.01 g / (m ² · 24 h) or less, and further, oxygen measured by a method according to JIS K 7126-1987. Permeability is 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less (1 atm is 1.01325 × 10 ⁵ Pa) Water vapor permeability is 10 ⁻³ g / (m ² · 24 h) or less Preferably, the water vapor permeability is 10 ⁻⁵ g / (m ² · 24 h) or less.
As a material for forming the barrier film, any material may be used as long as it has a function of suppressing entry of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like can be used. Further, in order to improve the brittleness of the film, it is more preferable to have a laminated structure of these inorganic layers and organic material layers. Although there is no restriction | limiting in particular about the lamination | stacking order of an inorganic layer and an organic layer, It is preferable to laminate | stack both alternately several times.
The method for forming the barrier film is not particularly limited. For example, the vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma weight A combination method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, and the like can be used. However, an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is particularly preferable.

  Examples of the opaque support substrate include metal plates such as aluminum and stainless steel, films, opaque resin substrates, and ceramic substrates.

The external extraction efficiency at room temperature of light emission of the organic EL device of the present invention is preferably 1% or more, more preferably 5% or more. Here, the external extraction quantum efficiency (%) = the number of photons emitted to the outside of the organic EL element / the number of electrons sent to the organic EL element × 100.
In addition, a hue improvement filter such as a color filter may be used in combination, or a color conversion filter that converts the emission color from the organic EL element into multiple colors using a phosphor may be used in combination. In the case of using a color conversion filter, the λmax of light emission of the organic EL element is preferably 480 nm or less.

<Sealing>
As a sealing means used for this invention, the method of adhere | attaching a sealing member, an electrode, and a support substrate with an adhesive agent can be mentioned, for example.
As a sealing member, it should just be arrange | positioned so that the display area | region of an organic EL element may be covered, and concave plate shape or flat plate shape may be sufficient. Further, transparency and electrical insulation are not particularly limited.
Specifically, a glass plate, a polymer plate (film), a metal plate (film), etc. are mentioned. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone. Examples of the metal plate include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
In the present invention, a polymer film and a metal film can be preferably used because the element can be thinned. Furthermore, the polymer film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 × 10 ⁻³ cm ³ / (m ² · 24 h · atm) or less, and conforms to JIS K 7129-1992. The water vapor permeability (25 ± 0.5 ° C., relative humidity (90 ± 2)% RH) measured by the above method is preferably 1 × 10 ⁻³ g / (m ² · 24 h) or less.
For processing the sealing member into a concave shape, sandblasting, chemical etching, or the like is used.

Specific examples of the adhesive include photocuring and thermosetting adhesives having reactive vinyl groups such as acrylic acid oligomers and methacrylic acid oligomers, and moisture curing adhesives such as 2-cyanoacrylates. be able to. Moreover, heat | fever and chemical curing types (two-component mixing), such as an epoxy type, can be mentioned. Moreover, hot-melt type polyamide, polyester, and polyolefin can be mentioned. Moreover, a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
In addition, since an organic EL element may deteriorate by heat processing, what can be adhesive-hardened from room temperature to 80 degreeC is preferable. A desiccant may be dispersed in the adhesive. Application | coating of the adhesive agent to a sealing part may use commercially available dispenser, and may print like screen printing.

In addition, it is also preferable that the electrode and the organic layer are coated on the outside of the electrode facing the support substrate with the organic layer interposed therebetween, and an inorganic or organic layer is formed in contact with the support substrate to form a sealing film. . In this case, the material for forming the film may be any material that has a function of suppressing intrusion of elements that cause deterioration of elements such as moisture and oxygen. For example, silicon oxide, silicon dioxide, silicon nitride, or the like may be used. it can.
Further, in order to improve the brittleness of the film, it is preferable to have a laminated structure of these inorganic layers and layers made of organic materials. The method for forming these films is not particularly limited. For example, vacuum deposition method, sputtering method, reactive sputtering method, molecular beam epitaxy method, cluster ion beam method, ion plating method, plasma polymerization method, atmospheric pressure plasma A polymerization method, a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used.

In the gap between the sealing member and the display area of the organic EL element, an inert gas such as nitrogen or argon, or an inert liquid such as fluorinated hydrocarbon or silicon oil can be injected in the gas phase and liquid phase. preferable. A vacuum is also possible.
Moreover, a hygroscopic compound can also be enclosed inside.
Examples of the hygroscopic compound include metal oxides (for example, sodium oxide, potassium oxide, calcium oxide, barium oxide, magnesium oxide, aluminum oxide) and sulfates (for example, sodium sulfate, calcium sulfate, magnesium sulfate, cobalt sulfate). Etc.), metal halides (eg calcium chloride, magnesium chloride, cesium fluoride, tantalum fluoride, cerium bromide, magnesium bromide, barium iodide, magnesium iodide etc.), perchloric acids (eg perchloric acid) Barium, magnesium perchlorate and the like), and anhydrous salts are preferably used in sulfates, metal halides and perchloric acids.

《Protective film, protective plate》
In order to increase the mechanical strength of the element, a protective film or a protective plate may be provided on the outer side of the sealing film on the side facing the support substrate with the organic layer interposed therebetween or on the sealing film. In particular, when the sealing is performed by the sealing film, the mechanical strength is not necessarily high, and thus it is preferable to provide such a protective film and a protective plate.
As a material that can be used for this, the same glass plate, polymer plate / film, metal plate / film, etc. used for the sealing can be used, but the polymer film is light and thin. Is preferably used.

《Light extraction》
The organic EL element emits light inside a layer having a refractive index higher than that of air (refractive index is about 1.7 to 2.1) and can extract only about 15% to 20% of the light generated in the light emitting layer. It is generally said. This is because light incident on the interface (interface between the transparent substrate and air) at an angle θ greater than the critical angle causes total reflection and cannot be taken out of the device, or between the transparent electrode or light emitting layer and the transparent substrate. This is because the light is totally reflected between the light and the light is guided through the transparent electrode or the light emitting layer, and as a result, the light escapes in the direction of the element side surface.
As a method for improving the light extraction efficiency, for example, a method of forming irregularities on the surface of the transparent substrate to prevent total reflection at the interface between the transparent substrate and the air (US Pat. No. 4,774,435), A method of improving efficiency by providing a light collecting property to a substrate (Japanese Patent Laid-Open No. 63-314795), a method of forming a reflective surface on a side surface of an element (Japanese Patent Laid-Open No. 1-220394), and light emission from a substrate A method of forming an antireflection film by introducing a flat layer having an intermediate refractive index between the bodies (Japanese Patent Laid-Open No. 62-172691), a flat having a lower refractive index between the substrate and the light emitter than the substrate A method of introducing a layer (Japanese Patent Laid-Open No. 2001-202827), a method of forming a diffraction grating between any one of a substrate, a transparent electrode layer and a light emitting layer (including between the substrate and the outside) (Japanese Patent Laid-Open No. 11-283951) Gazette).

In the present invention, these methods can be used in combination with the organic EL device of the present invention. However, a method of introducing a flat layer having a lower refractive index than the substrate between the substrate and the light emitter, or a substrate, transparent A method of forming a diffraction grating between any layers of the electrode layer and the light emitting layer (including between the substrate and the outside) can be suitably used.
In the present invention, by combining these means, it is possible to obtain an element having higher luminance or durability.
When a medium having a low refractive index is formed between the transparent electrode and the transparent substrate with a thickness longer than the wavelength of light, the light extracted from the transparent electrode has a higher extraction efficiency to the outside as the refractive index of the medium is lower.
Examples of the low refractive index layer include aerogel, porous silica, magnesium fluoride, and a fluorine-based polymer. Since the refractive index of the transparent substrate is generally about 1.5 to 1.7, the low refractive index layer preferably has a refractive index of about 1.5 or less. Further, it is preferably 1.35 or less.
The thickness of the low refractive index medium is preferably at least twice the wavelength in the medium. This is because the effect of the low refractive index layer is diminished when the thickness of the low refractive index medium is about the wavelength of light and the electromagnetic wave that has exuded by evanescent enters the substrate.

The method of introducing a diffraction grating into an interface or any medium that causes total reflection is characterized by a high effect of improving light extraction efficiency. This method uses the property that the diffraction grating can change the direction of light to a specific direction different from refraction by so-called Bragg diffraction such as first-order diffraction and second-order diffraction. Light that cannot be emitted due to total internal reflection between layers is diffracted by introducing a diffraction grating in any layer or medium (in a transparent substrate or transparent electrode), and the light is removed. I want to take it out.
The introduced diffraction grating desirably has a two-dimensional periodic refractive index. This is because light emitted from the light-emitting layer is randomly generated in all directions, so in a general one-dimensional diffraction grating having a periodic refractive index distribution only in a certain direction, only light traveling in a specific direction is diffracted. Therefore, the light extraction efficiency does not increase so much. However, by making the refractive index distribution a two-dimensional distribution, light traveling in all directions is diffracted, and light extraction efficiency is increased.
As described above, the position where the diffraction grating is introduced may be in any of the layers or in the medium (in the transparent substrate or in the transparent electrode), but is preferably in the vicinity of the organic light emitting layer where light is generated.
At this time, the period of the diffraction grating is preferably about 1/2 to 3 times the wavelength of light in the medium.
The arrangement of the diffraction grating is preferably two-dimensionally repeated, such as a square lattice, a triangular lattice, or a honeycomb lattice.

<Condenser sheet>
The organic EL device of the present invention is processed on the light extraction side of the substrate so as to provide, for example, a microlens array structure, or combined with a so-called condensing sheet, for example, with respect to a specific direction, for example, the device light emitting surface. By condensing in the front direction, the luminance in a specific direction can be increased.
As an example of the microlens array, quadrangular pyramids having a side of 30 μm and an apex angle of 90 degrees are two-dimensionally arranged on the light extraction side of the substrate. One side is preferably 10 μm to 100 μm. If it becomes smaller than this, the effect of diffraction will generate | occur | produce and color, and if too large, thickness will become thick and is not preferable.
As the condensing sheet, for example, a sheet that is put into practical use in an LED backlight of a liquid crystal display device can be used. As such a sheet, for example, a brightness enhancement film (BEF) manufactured by Sumitomo 3M Limited can be used. As the shape of the prism sheet, for example, the base material may be formed by forming a △ -shaped stripe having a vertex angle of 90 degrees and a pitch of 50 μm, or the vertex angle is rounded and the pitch is changed randomly. Other shapes may be used.
Moreover, in order to control the light emission angle from a light emitting element, you may use together a light diffusing plate and a film with a condensing sheet. For example, a diffusion film (light-up) manufactured by Kimoto Co., Ltd. can be used.

<< Method for producing organic EL element >>
As an example of the method for producing the organic EL device of the present invention, a method for producing an organic EL device comprising an anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode will be described.

First, a desired electrode material, for example, a thin film made of a material for an anode is formed on a suitable support substrate by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm. To do.
Next, an organic compound thin film of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a hole blocking layer, which are organic EL element materials, is formed thereon.
As a method for forming each of these layers, there are a vapor deposition method, a wet process (spin coating method, casting method, ink jet method, printing method) and the like as described above, but a uniform film is easily obtained and pinholes are not easily generated. In view of the above, in the present invention, a wet process is preferable, and film formation by a coating method such as a spin coating method, an ink jet method, or a printing method is particularly preferable.
Examples of the liquid medium for dissolving or dispersing the organic EL material according to the present invention include ketones such as methyl ethyl ketone and cyclohexanone, fatty acid esters such as ethyl acetate, halogenated hydrocarbons such as dichlorobenzene, toluene, xylene, and mesitylene. Aromatic hydrocarbons such as cyclohexylbenzene, aliphatic hydrocarbons such as cyclohexane, decalin, and dodecane, and organic solvents such as DMF and DMSO can be used. Moreover, as a dispersion method, it can disperse | distribute by dispersion methods, such as an ultrasonic wave, high shear force dispersion | distribution, and media dispersion | distribution.
After these layers are formed, a thin film made of a cathode material is formed thereon by 1 μm or less, preferably by a method such as vapor deposition or sputtering so that the film thickness is in the range of 50 nm to 200 nm. By providing, a desired organic EL element can be obtained.
In addition, it is also possible to reverse the production order and produce the cathode, the electron injection layer, the electron transport layer, the light emitting layer, the hole transport layer, the hole injection layer, and the anode in this order.
When a DC voltage is applied to the multicolor display device thus obtained, light emission can be observed by applying a voltage of about 2 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. An alternating voltage may be applied. The alternating current waveform to be applied may be arbitrary.

<Application>
The organic EL element of the present invention can be used as a display device, a display, and various light emission sources.
For example, lighting devices (home lighting, interior lighting), clock and liquid crystal backlights, billboard advertisements, traffic lights, light sources of optical storage media, light sources of electrophotographic copying machines, light sources of optical communication processors, light Although the light source of a sensor etc. are mentioned, It is not limited to this, Especially, it can use effectively for the use as a backlight of a liquid crystal display device, and a light source for illumination.
In the organic EL element of the present invention, patterning may be performed by a metal mask, an ink jet printing method, or the like as needed during film formation.
In the case of patterning, only the electrode may be patterned, the electrode and the light emitting layer may be patterned, or the entire layer of the element may be patterned. In the fabrication of the element, a conventionally known method is used. Can do.

The light emission color of the organic EL device of the present invention and the compound according to the present invention is shown in FIG. 4.16 on page 108 of “New Color Science Handbook” (edited by the Japan Color Society, University of Tokyo Press, 1985). It is determined by the color when the result measured with the total CS-1000 (manufactured by Konica Minolta Sensing) is applied to the CIE chromaticity coordinates.
When the organic EL element of the present invention is a white element, white means that the chromaticity in the CIE1931 color system at 1000 cd / m ² is X when the 2 ° viewing angle front luminance is measured by the above method. = 0.33 ± 0.07 and Y = 0.33 ± 0.1.

  The present invention will be further illustrated by showing specific embodiments, but of course the scope of the present invention is not limited thereto.

<< Production of Organic EL Element 1-1 >>
An organic EL element was produced as follows.
Transparent support provided with this ITO transparent electrode after patterning on a substrate (NH45 manufactured by NH Techno Glass) made of ITO (indium tin oxide) with a thickness of 100 nm on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode The substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.

Thereafter, this transparent support substrate is fixed to a substrate holder of a commercially available vacuum deposition apparatus, while 200 mg of α-NPD is put into a molybdenum resistance heating boat, and 200 mg of CBP is put into another resistance heating boat made of molybdenum. 100 mg of phosphorescent compound Ir (ppy) ₃ is put into a resistance heating boat, 200 mg of bathocuproin (BCP) is put into another molybdenum resistance heating boat, and 200 mg of Alq ₃ is put into another resistance heating boat made of molybdenum. Attached to the vapor deposition equipment.

Thereafter, the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, heated by energizing the heating boat containing α-NPD, and deposited on a transparent support substrate at a deposition rate of 0.1 nm / sec. The hole transport layer was provided.
Further, the heating boat containing CBP and the phosphorescent compound Ir (ppy) ₃ is energized and heated, and is co-deposited on the hole transport layer at a deposition rate of 0.2 nm / sec and 0.012 nm / sec, respectively. Thus, a light emitting layer having a thickness of 35 nm was provided.
Further, an electron transport layer that also serves as a hole blocking function with a film thickness of 10 nm is provided by energizing and heating the heating boat containing BCP and depositing on the light emitting layer at a deposition rate of 0.1 nm / sec. It was.
On top of that, the heating boat containing Alq ₃ was further energized and heated, and was deposited on the electron transport layer at a deposition rate of 0.1 nm / sec to provide an electron injection layer having a thickness of 40 nm. .
In addition, the substrate temperature at the time of formation (at the time of vapor deposition) of a positive hole transport layer, a light emitting layer, an electron carrying layer, and an electron injection layer was made into room temperature.
Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the "organic EL element 1-1" was produced.

<< Production of Organic EL Elements 1-2 to 1-34 >>
In the production of the organic EL element 1-1, CBP of the light emitting layer was replaced with the compounds shown in Table 1 as shown in Table 1.
Other than that produced "organic EL element 1-2 to 1-34" similarly.
In addition, the following were used as the comparative compounds 1-5.

<< Evaluation of organic EL elements >>
The organic EL element was evaluated as follows.
The evaluation results are shown in Table 1.

(1) Luminous efficiency The organic EL element 1-1 began to flow at an initial driving voltage of 3 V, and showed green light emission from the phosphorescent compound that is a dopant of the light emitting layer.
About each organic EL element containing the said organic EL element 1-1, the luminous efficiency (lm / W) when a 10-V DC voltage was applied in 23 degreeC and dry nitrogen gas atmosphere was measured. The measurement result of the luminous efficiency was expressed as a relative value when the organic EL element 1-1 was set to 100.

(2) Durability For each organic EL element, when it was driven at a constant current of ^2.5 mA / cm ² , the time (half-life time) required for the initial luminance to drop to half of the original was measured. Durability was evaluated as an index.
The half-life time is expressed as a relative value when the organic EL element 1-1 is 100.

(3) Drive voltage Each organic EL element was driven at a constant current of ^2.5 mA / cm ² at room temperature (about 23 to 25 ° C.), and the voltage at that time was measured.
As shown below, the measurement result of each organic EL element is shown as a relative value with the organic EL element 1-1 (comparison) as 100.
Drive voltage = (initial drive voltage of each element / initial drive voltage of the organic EL element 1-1) × 100
In addition, it shows that a drive voltage is so small with respect to a comparative example (organic EL element 1-1) that a relative value is small.

(4) Time-dependent change of drive voltage Each organic EL element was continuously lit at a constant current of ^2.5 mA / cm ² at room temperature, and the drive voltage was measured when the brightness reached 70% of the initial brightness. .
The measurement results of each organic EL element are shown as relative values so that the organic EL element 1-1 (comparison) becomes 100 as shown below.
Drive voltage change 1 = Drive voltage when the luminance of the organic EL element 1-1 is 70% / Initial drive voltage of the organic EL element 1-1. Drive voltage change of each element = Drive voltage when the brightness of each element is 70% / Each element Initial drive voltage of drive voltage change (τ ^1/7 ) = change in drive voltage of each element / change in drive voltage 1 × 100

(5) Summary As shown in Table 1, when comparing the organic EL elements 1-1 to 1-6 and the organic EL elements 1-7 to 1-34, the organic EL elements 1-7 to 1-34 have the luminous efficiency. It can be seen that it has excellent durability and high durability, and that the driving voltage and its rate of change with time have also decreased.
From the above, the use of the compound of general formula (1) or general formula (2) as a host compound realizes improvement in luminous efficiency, long emission life, reduction in driving voltage, and suppression of voltage increase during driving. This proves useful.
Further, it can be seen that if the organic EL element material is in a more preferable mode (for example, a preferable substituent, the number of the substituents, etc.), both higher efficiency and life can be achieved.

The phosphorescent compound Ir (ppy) ₃ of the organic EL device 1-1 of Example 1 was replaced with Ir-15, and CBP was replaced with the compounds shown in Table 2.
Otherwise, “organic EL elements 2-1 to 2-34” were produced in exactly the same manner.
With respect to these elements exhibiting blue light emission, the light emission efficiency, durability, drive voltage, and rate of change with time were measured in the same manner as in Example 1. The obtained results are shown in Table 2.

  As shown in Table 2, even when the type of phosphorescent compound was changed and the emission color was changed, the same result as in Example 1 was obtained, and in particular, the emission lifetime was significantly improved.

The hole transport layer and the electron transport layer of the organic EL device 1-1 of Example 1 were replaced with the compounds shown in Table 3.
Otherwise, “organic EL elements 3-1 to 3-25” were produced in exactly the same manner.
With respect to these elements exhibiting green light emission, the light emission efficiency, durability, drive voltage, and change rate with time were measured in the same manner as in Example 1. The obtained results are shown in Table 3.

  As shown in Table 3, even if the compound of the general formula (1) or the general formula (2) is contained in the hole transport layer or the electron transport layer, the light emission efficiency is improved, the light emission life is prolonged, and the driving voltage is lowered. It can be seen that suppression of voltage rise during driving can be realized.

In organic EL element 1-7 (green light-emitting organic EL element) produced in Example 1, organic EL element 2-7 (blue light-emitting organic EL element) produced in Example 2, and organic EL element 1-7 An organic EL element 4-7 (red light emitting organic EL element) produced in the same manner as the organic EL element 1-1 except that the light compound Ir (ppy) ₃ was replaced with Ir-9 was placed in parallel on the same substrate. The active matrix type full-color display device 1 shown in FIG.

FIG. 2 shows only a schematic diagram of the display portion A of the produced full-color display device 1.
As shown in FIG. 2, the display unit A includes a wiring unit including a plurality of scanning lines 5 and data lines 6 and a plurality of pixels 3 juxtaposed on the same substrate (pixels whose emission color is a red region, green region pixels). , Blue region pixels, etc.). Each of the scanning lines 5 and the plurality of data lines 6 in the wiring portion is made of a conductive material. The scanning lines 5 and the data lines 6 are orthogonal to each other in a grid pattern, and are connected to the pixels 3 at the orthogonal positions (details are not shown).
The plurality of pixels 3 are driven by an active matrix system in which an organic EL element corresponding to each emission color, a switching transistor as an active element, and a driving transistor are provided. When a scanning signal is applied from the scanning line 5, an image data signal is received from the data line 6, and light is emitted in accordance with the received image data. In this way, full color display is possible by juxtaposing the red, green, and blue pixels 3 appropriately.
Actually, when the full-color display device 1 manufactured using the organic EL element 1-7, the organic EL element 2-7, and the organic EL element 4-7 is driven, the luminance is high at low voltage and the durability is good. A clear full-color video display was obtained.
According to the above Example 4, the organic EL element 1-7 containing an iridium complex (Ir (ppy) ₃ ) serving as a green luminescence source and the organic containing an iridium complex (Ir-15) serving as a blue luminescence source. It can be seen that if the EL element 2-7 and an organic EL element containing an iridium complex (Ir-9) serving as a red light emission source are arranged in parallel as the pixel 3, a full-color display device can be configured.

In addition, red light emitting organic EL element 4-7, organic EL elements 1-8 to 1-34 as green light emitting organic EL elements, and organic EL elements 2-8 to 2-34 as blue light emitting organic EL elements Even when randomly combined, full color display was possible.
Further, as the red light emitting organic EL elements, all of the organic EL elements 4-8 to 4-34 in which the phosphorescent compound Ir (ppy) ₃ of the organic EL elements 1-8 to 1-34 is replaced with Ir-9, The red organic EL device was excellent in light emission luminance, light emission efficiency, drive voltage, and rate of change with time.

In Example 5, a white light-emitting organic EL element was produced, and it was confirmed whether or not the organic EL element could be applied as a lighting device.
First, after patterning on a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) formed by depositing 100 nm of ITO (indium tin oxide) on a glass substrate of 100 mm × 100 mm × 1.1 mm as an anode, this ITO transparent electrode was formed. The provided transparent support substrate was ultrasonically cleaned with isopropyl alcohol, dried with dry nitrogen gas, and subjected to UV ozone cleaning for 5 minutes.
Thereafter, a solution obtained by diluting poly (3,4-ethylenedioxythiophene) -polystyrene sulfonate (PEDOT / PSS, Bayer, Baytron P Al 4083) with pure water to 70% on this transparent support substrate at 3000 rpm, After forming into a film by a spin coat method in 30 seconds, it dried at 200 degreeC for 1 hour, and provided the positive hole transport layer with a film thickness of 30 nm.
Then, this board | substrate was moved to nitrogen atmosphere, and exemplary compound 2-123 (60 mg) and Ir (ppy) ₃ (1.2 mg), Ir-15 (12 as phosphorescent compounds) on a positive hole transport layer. 0.0 mg) and Ir-9 (1.2 mg) were dissolved in 6 ml of toluene, and a film was formed by spin coating under conditions of 1000 rpm and 30 seconds. Heating was performed in vacuum at 150 ° C. for 1 hour to form a light emitting layer.
Furthermore, using a solution of BCP (20 mg) dissolved in 6 ml of cyclohexane, a film was formed by spin coating under conditions of 1000 rpm and 30 seconds. Heating was performed in vacuum at 80 ° C. for 1 hour to form a first electron transport layer.

Subsequently, this substrate was fixed to a substrate holder of a vacuum vapor deposition apparatus, and 200 mg of Alq ₃ was put into a molybdenum resistance heating boat and attached to the vacuum vapor deposition apparatus. After depressurizing the vacuum chamber to 4 × 10 ⁻⁴ Pa, energize and heat the heating boat containing Alq ₃ , and deposit on the first electron transport layer at a deposition rate of 0.1 nm / second, Further, a second electron transport layer having a thickness of 40 nm was provided.
The substrate temperature at the time of forming the second electron transport layer (during vapor deposition) was room temperature.
Then, 0.5 nm of lithium fluoride and 110 nm of aluminum were vapor-deposited, the cathode was formed, and the white light emitting organic EL element was produced.

When this white light-emitting organic EL element was energized, almost white light was obtained, and it was found that the organic EL element can be used as a lighting device.
According to the above Example 5, if an organic EL element containing an iridium complex (Ir (ppy) ₃ , Ir-15, Ir-9) serving as a green, blue and red light source is used, a lighting device is configured. I can understand.
Of course, an organic EL element containing an iridium complex (Ir (ppy) ₃ ) serving as a green emission source, an organic EL element containing an iridium complex (Ir-15) serving as a blue emission source, and iridium serving as a red emission source Even when the organic EL element containing the complex (Ir-9) is laminated, white light emission can be obtained, and this can be configured as a lighting device.
In addition, it turned out that white light emission is obtained similarly even if the illustration compound 2-123 which comprises a light emitting layer is replaced with another compound.

DESCRIPTION OF SYMBOLS 1 Full color display device 3 Pixel 5 Scan line 6 Data line A Display part B Control part

Claims (10)

An organic electroluminescence device material comprising a compound represented by the general formula (1) or the general formula (2).

In formula (1), “X ₁ ” and “Y ₁ ” each independently represent any of N, P, P═O, P═S, SiAr ₁ , and “Z ₁ ” is a simple bond or NAr ₂ , O, S, PAr ₃ , P (═O) Ar ₄ , P (═S) Ar ₅ , or SiAr ₆ Ar ₇ .
“Ar _{1 to} Ar ₇ ” represents an aromatic hydrocarbon group or an aromatic heterocyclic group.
“A _{1 to} A ₁₄ ” each independently represent C—R _x1 or N, and the plurality of R _x1 may be the same or different.
“R _x1 ” each independently represents a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an alkoxyl group, a cycloalkoxyl group, Aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, amide group, carbamoyl group, sulfinyl group, alkylsulfonyl group or arylsulfonyl Group, amino group, nitro group, cyano group, hydroxyl group, alkylsilyl group or arylsilyl group, alkylphosphino group or arylphosphino group, alkylphosphoryl group or arylphosphoryl group, alkylthiophosphoryl group or aryl group Is any group selected from Ruchiohosuhoriru group.

In the formula (2), “X ₂ ” and “Y ₂ ” each independently represent a group having the same meaning as X ₁ and Y ₁ in the general formula (1), and “Z ₂ ” in the general formula (1) A group having the same meaning as Z ₁ is represented.
“A _{15 to} A ₂₈ ” each independently represent C—R _x2 or N, and the plurality of R _x2 may be the same or different.
“R _x2 ” each independently represents a group having the same _meaning as R _x1 in formula (1). In the organic electroluminescent element material according to claim 1,
The organic electroluminescence element material, wherein Z _{1 in the} general formula (1) or Z _{2 in the} general formula (2) is a mere bond. The anode,
A cathode,
At least one organic layer including a light emitting layer, the organic layer sandwiched between the anode and the cathode;
In an organic electroluminescence device comprising:
At least 1 layer of the said organic layer contains the compound represented by General formula (1) or General formula (2), The organic electroluminescent element characterized by the above-mentioned.

In formula (1), “X ₁ ” and “Y ₁ ” each independently represent any of N, P, P═O, P═S, SiAr ₁ , and “Z ₁ ” is a simple bond or NAr ₂ , O, S, PAr ₃ , P (═O) Ar ₄ , P (═S) Ar ₅ , or SiAr ₆ Ar ₇ .
“Ar _{1 to} Ar ₇ ” represents an aromatic hydrocarbon group or an aromatic heterocyclic group.
“A _{1 to} A ₁₄ ” each independently represent C—R _x1 or N, and the plurality of R _x1 may be the same or different.
“R _x1 ” each independently represents a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, a heterocyclic group, an aromatic heterocyclic group, a halogen atom, an alkoxyl group, a cycloalkoxyl group, Aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, sulfamoyl group, ureido group, acyl group, acyloxy group, amide group, carbamoyl group, sulfinyl group, alkylsulfonyl group or arylsulfonyl Group, amino group, nitro group, cyano group, hydroxyl group, alkylsilyl group or arylsilyl group, alkylphosphino group or arylphosphino group, alkylphosphoryl group or arylphosphoryl group, alkylthiophosphoryl group or aryl group Is any group selected from Ruchiohosuhoriru group.

In the formula (2), “X ₂ ” and “Y ₂ ” each independently represent a group having the same meaning as X ₁ and Y ₁ in the general formula (1), and “Z ₂ ” in the general formula (1) A group having the same meaning as Z ₁ is represented.
“A _{15 to} A ₂₈ ” each independently represent C—R _x2 or N, and the plurality of R _x2 may be the same or different.
“R _x2 ” each independently represents a group having the same _meaning as R _x1 in formula (1). In the organic electroluminescent element according to claim 3,
The organic electroluminescent element, wherein Z _{1 in the} general formula (1) or Z _{2 in the} general formula (2) is a mere bond. In the organic electroluminescent element according to claim 3 or 4,
The said light emitting layer contains the compound represented by the said General formula (1) or General formula (2), The organic electroluminescent element characterized by the above-mentioned. In the organic electroluminescent element according to any one of claims 3 to 5,
The organic light-emitting device, wherein the light-emitting layer contains a phosphorescent metal complex. The organic electroluminescence device according to claim 6,
An organic electroluminescence device, wherein the phosphorescent metal complex is an iridium complex. In the organic electroluminescent element according to any one of claims 3 to 7,
An organic electroluminescence device, wherein the organic layer is produced by a wet process.   A display device comprising the organic electroluminescence element according to claim 3.   It has an organic electroluminescent element as described in any one of Claims 3-8, The illuminating device characterized by the above-mentioned.

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