JP5621482B2 - Organometallic complex, organometallic complex-containing composition, light emitting material, organic electroluminescent element material, organic electroluminescent element, organic electroluminescent display device, and organic electroluminescent lighting device - Google Patents

Description

  The present invention relates to an organometallic complex, and more specifically, an organometallic complex used for a light emitting layer of an organic electroluminescent element, a luminescent material or an organic electroluminescent element material composed of the organometallic complex, the organometallic complex and a solvent. The present invention relates to a composition to be contained, an organic electroluminescent element using the organometallic complex, a display device or a lighting device including the organic electroluminescent element.

  In recent years, organic electroluminescent elements using organic thin films have been developed as thin film type electroluminescent elements instead of using inorganic materials. Organic electroluminescence devices usually have a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, etc. between the anode and the cathode, and light emission of red, green, blue, etc. suitable for each layer. Device development is progressing.

  In addition, as a method for forming each layer of the organic electroluminescent element, there are a vapor deposition film forming method and a wet film forming method. The vapor deposition method has a problem in terms of yield when manufacturing a medium or large full color panel for a television or a monitor. Therefore, the wet film forming method is suitable for these large-area applications.

  However, in order to form each layer of the organic electroluminescent element by the wet film forming method, it has been desired that the material for forming each layer is dissolved in a solvent and has high performance as an element even after the wet film formation. However, many materials (see Patent Document 1) that have been used in a conventionally developed vapor deposition film forming method are not suitable for the wet film forming method.

International Publication No. 2006/014599 Pamphlet

  The present invention has been made in view of the above-described conventional situation, and an object thereof is to provide an organometallic complex that has high solubility and dispersibility in a solvent and is suitable for wet film formation. It is another object of the present invention to provide an organometallic complex in which the obtained organic electroluminescent device can maintain high performance in terms of life and durability even when used in an organic layer formed by a wet film formation method. .

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an organometallic complex having a phenylquinoline ring having a specific substituent has high solubility in a solvent and has a lifetime as a phosphorescent dopant of an organic electroluminescent device. And the present invention has been found.

That is, the gist of the present invention resides in the following [1] to [10].
[1] An organometallic complex represented by the following formula (1).

[In Formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, an optionally substituted hydrocarbon group, an optionally substituted alkoxy group, or a substituted group. An aromatic heterocyclic group which may have a group or a silyl group having a substituent, and these groups may be bonded to each other to form a ring, but any one of R ^{1 to} R ¹⁰ One is a group having an alkyl group having 5 or more carbon atoms which may have a substituent. ]

[2] The organic material according to [1], wherein in formula (1), any one of R ^{1 to} R ¹⁰ is a phenyl group having an alkyl group having 5 or more carbon atoms which may have a substituent. Metal complex.
[3] The organometallic complex according to [1] or [2], wherein in formula (1), R ³ is a phenyl group having an alkyl group having 5 or more carbon atoms which may have a substituent.
[4] A luminescent material comprising the organometallic complex according to any one of [1] to [3].
[5] An organic electroluminescent element material comprising the organometallic complex according to any one of [1] to [3].
[6] An organometallic complex-containing composition comprising the organometallic complex according to any one of [1] to [3] and a solvent.
[7] An organic electroluminescence device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, wherein the organic layer is an organic metal according to any one of the above [1] to [3] An organic electroluminescent device comprising a complex.
[8] The organic electroluminescent element as described in [7] above, wherein the organic layer is a light emitting layer.
[9] An organic electroluminescent display device comprising the organic electroluminescent element as described in [7] or [8] above.
[10] An organic electroluminescent illumination device comprising the organic electroluminescent element as described in [7] or [8] above.

  According to the present invention, an organometallic complex having high solubility and dispersibility in a solvent and suitable for wet film formation can be provided. In addition, the organic electroluminescent device using the organometallic complex has a high performance in terms of life and durability even if the organic electroluminescent device is an organic layer formed by a wet film forming method. Can do.

Schematic of a cross section showing an example of the structure of the organic electroluminescent element of the present invention

The description of the constituent requirements described below is an example (representative example) of an embodiment of the present invention, and the present invention is not limited to these contents.
The present invention relates to an organometallic complex represented by the following formula (1) and use thereof.

In formula (1), R ^{1 to} R ¹⁰ are each independently a hydrogen atom, a halogen atom, a hydrocarbon group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An aromatic heterocyclic group which may have a silyl group or a silyl group having a substituent, and these groups may be bonded to each other to form a ring, but any one of R ^{1 to} R ¹⁰ Is a group having an alkyl group having 5 or more carbon atoms which may have a substituent.

As described above, the organometallic complex of the present invention is a group having an alkyl group having 5 or more carbon atoms in which any one of R ^{1 to} R ¹⁰ may have a substituent in formula (1). It has one characteristic. Thereby, the solubility is improved, the molecules are dispersed well, the problem of crystallization over time is less likely to occur, and it is presumed that the effect of improving the lifetime and durability is expected.

<Specific Examples of Groups in R ^{1 to} R ¹⁰ >
In the organometallic complex represented by the formula (1) of the present invention, atoms and groups in the definition of R ^{1 to} R ¹⁰ will be specifically described.

  Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Of these, fluorine is preferred.

Examples of the hydrocarbon group include a saturated hydrocarbon group, an unsaturated hydrocarbon group, and an aromatic hydrocarbon group.
Here, an alkyl group is mentioned as a saturated hydrocarbon group.
The alkyl group usually has 1 or more carbon atoms, preferably 3 or more, more preferably 5 or more, and usually 15 or less, preferably 12 or less, more preferably 8 or less. If the lower limit is not reached, the solubility may be insufficient. If the upper limit is exceeded, there is a risk of oxidative degradation during heat treatment. It may be a linear alkyl group, a branched alkyl group, or a cycloalkyl group. Specifically, for example, methyl group, ethyl group, propyl group, iso-propyl group, butyl group, iso-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, cyclohexyl group , Alkyl groups such as decyl group and octadecyl group.

Further, examples of the unsaturated hydrocarbon group include an alkenyl group and an alkynyl group.
The alkenyl group usually has 2 or more carbon atoms, preferably 3 or more, more preferably 5 or more, and usually 12 or less, preferably 10 or less, more preferably 8 or less. If it is below the lower limit, the solubility may be insufficient, and if it exceeds the upper limit, it may be oxidized and deteriorated during heat treatment. Specific examples include a vinyl group, an allyl group, and a hexenyl group.

  The alkynyl group usually has 2 or more carbon atoms, preferably 3 or more, and usually 8 or less, preferably 5 or less, more preferably 3 or less. If it is below the lower limit, the solubility may be insufficient, and if it exceeds the upper limit, it may be oxidized and deteriorated during heat treatment. Specific examples include an acetylenyl group and a propynyl group.

  The aromatic hydrocarbon group usually has 5 or more carbon atoms, preferably 6 or more, and usually 16 or less, preferably 14 or less, more preferably 10 or less. If the lower limit is not reached, the stability may be deteriorated, and if the upper limit is exceeded, the complex may not be formed easily. Among these, an aromatic hydrocarbon group derived from a 6-membered monocyclic ring or a 2-5 condensed ring is preferable. Specific examples include groups derived from aromatic hydrocarbons such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, and fluoranthene ring. It is done. In particular, a group derived from a benzene ring (phenyl group) is preferable.

  The alkoxy group usually has 1 or more carbon atoms, preferably 2 or more, and usually 12 or less, preferably 10 or less, more preferably 8 or less. If it is below the lower limit, the solubility may be insufficient, and if it exceeds the upper limit, it may be oxidized and deteriorated during heat treatment. Specific examples include alkoxy groups such as a methoxy group, an ethoxy group, a pentyloxy group, a hexyloxy group, an octyloxy group, an isopropyloxy group, a cyclohexyloxy group, and an octadecyloxy group.

  The aromatic heterocyclic group usually has 3 or more carbon atoms, preferably 4 or more, more preferably 5 or more, and usually 15 or less, preferably 12 or less, more preferably 8 or less. If the lower limit is not reached, the stability of the complex may be impaired. If the upper limit is exceeded, the complex may not be formed. Specifically, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole Ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, Examples include groups derived from aromatic heterocycles such as isoquinoline ring, sinoline ring, quinoxaline ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.

  As the silyl group having a substituent, a silyl group having a hydrocarbon group or an aromatic hydrocarbon group is preferable, and a silyl group having a hydrocarbon group is more preferable. Specific examples and preferred groups of the hydrocarbon group and aromatic hydrocarbon group include the same groups as described above. Furthermore, the silyl group having a substituent is preferably a silyl group having an alkyl group, and the silyl group having an alkyl group is preferably a trialkylsilyl group. Specifically, for example, a trimethylsilyl group, a triethylsilyl group, t -Butylsilyl group, triphenylsilyl group and the like.

Of these halogen atoms, hydrocarbon groups, alkoxy groups, aromatic heterocyclic groups, and substituted silyl groups in R ^{1 to} R ¹⁰ , an alkyl group or an aromatic hydrocarbon group is preferable. Moreover, when R < ¹ > -R < ¹⁰ > is a silyl group which has a hydrocarbon group, an alkoxy group, an aromatic heterocyclic group, or a substituent, these groups may have a substituent.

Here, examples of the substituent that R ^{1 to} R ¹⁰ may have include an alkyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group, an alkoxy group, a (hetero) aryloxy group, an alkylthio group, (hetero ) Organic groups such as arylthio group, cyano group, amino group, and silyl group having a substituent. Among these, an alkyl group and an aromatic hydrocarbon group are preferable from the viewpoint of stability of the compound, and an aromatic hydrocarbon group is particularly preferable. In addition, the said (hetero) aryl shows both aryl and heteroaryl.

  The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms. Specifically, for example, a methyl group, an ethyl group, a propyl group, an iso-propyl group, a butyl group, an iso-butyl group, a sec-butyl group. Tert-butyl group, pentyl group, hexyl group, octyl group, cyclohexyl group, decyl group, octadecyl group and the like. Among them, pentyl groups such as n-pentyl group, hexyl groups such as n-hexyl group and 2-ethylhexyl group are preferable because they have high solubility in nonpolar solvents.

  As the aromatic hydrocarbon group, an aromatic hydrocarbon group having 6 to 25 carbon atoms is preferable, and an aromatic hydrocarbon group derived from a 6-membered monocyclic ring or a 2-5 condensed ring is preferable. Specific examples include groups derived from aromatic hydrocarbons such as a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, and fluoranthene ring. It is done.

  The aromatic heterocyclic group is preferably an aromatic hydrocarbon group having 3 to 20 carbon atoms. Specifically, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole Ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, Examples include groups derived from aromatic heterocycles such as isoquinoline ring, sinoline ring, quinoxaline ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring.

  As this alkoxy group, a C1-C20 alkoxy group is preferable, and a methoxy group, an ethoxy group, an isopropyloxy group, a cyclohexyloxy group, an octadecyloxy group etc. are mentioned specifically, for example.

  The (hetero) aryloxy group is preferably a (hetero) aryloxy group having 3 to 20 carbon atoms, specifically, for example, phenoxy group, 1-naphthyloxy group, 9-anthranyloxy group, 2-thienyl. An oxy group etc. are mentioned.

  The alkylthio group is preferably an alkylthio group having 1 to 20 carbon atoms, and specific examples include a methylthio group, an ethylthio group, an isopropylthio group, a cyclohexylthio group, and the like.

  The (hetero) arylthio group is preferably a (hetero) arylthio group having 3 to 20 carbon atoms. Specific examples include a phenylthio group, a 1-naphthylthio group, a 9-anthranylthio group, and a 2-thienylthio group. It is done.

  The silyl group having a substituent is preferably a silyl group having an alkyl group, and the silyl group having an alkyl group is preferably a trialkylsilyl group. Specific examples include, for example, a trimethylsilyl group, a triethylsilyl group, t- A butylsilyl group, a triphenylsilyl group, etc. are mentioned.

R ^{1 to} R ¹⁰ may be bonded to each other, preferably bonded to an adjacent group to form a ring. In this case, a bond between carbon atoms is preferable, and a bond between ends of the alkyl group is more preferable.

As described above, any one of R ^{1 to} R ¹⁰ is a group having an alkyl group having 5 or more carbon atoms, which may have a substituent. R ³ is preferably a group having the alkyl group. Specific examples and preferred groups of the substituent that the group having an alkyl group may have include those described above.

Further, the alkyl group having 5 or more carbon atoms is a linear, branched or cyclic alkyl group having 5 or more carbon atoms, and the lower limit of the carbon number is preferably 6 or more, more preferably 8 or more. Moreover, as an upper limit of carbon number, Preferably it is 15 or less, More preferably, it is 12 or less. From the viewpoint of solubility in an organic solvent, the alkyl group having 5 or more carbon atoms is particularly preferably one having a main chain of the alkyl group having 5 or more carbon atoms.
Specific examples of the alkyl group having 5 or more carbon atoms are preferably straight-chain alkyl groups, and examples thereof include an n-pentyl group, an n-hexyl group, and an n-octyl group.

As described above, specific examples of the substituent of the alkyl group include those exemplified as the substituents of R ^{1 to} R ¹⁰ , but when the alkyl group having 5 or more carbon atoms is unsubstituted, The effect is more remarkable. The group having an alkyl group having 5 or more carbon atoms is preferably a phenyl group having an alkyl group having 5 or more carbon atoms.

Furthermore, in General formula (1), as R < ¹ >, R < ⁴ >, R < ⁷ >, R <^9> , R < ¹⁰ >, a hydrogen atom is particularly preferable. R ² is particularly preferably a hydrogen atom, an alkyl group, an alkoxy group, a halogen atom, an alkyl group or an alkenyl group substituted with a halogen atom. R ⁵ is particularly preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, a halogen atom or an alkyl group substituted with a halogen atom. R ⁶ is particularly preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group, a halogen atom, an alkyl group substituted with a halogen atom, an aromatic hydrocarbon group, or a trialkylsilyl group. R ⁸ is particularly preferably a hydrogen atom, an alkyl group, an alkoxy group, an alkenyl group or a trialkylsilyl group. In addition, when R ⁵ and R ⁶ are an alkyl group or an alkenyl group, those which are bonded to each other to form a ring are also preferable.

As described above, in the formula (1), any one of R ^{1 to} R ¹⁰ is particularly preferably a phenyl group having an alkyl group having 5 or more carbon atoms which may have a substituent. By having a phenyl group in the p-position with respect to the coordination position to Ir, the stability of the hybrid orbital due to the d orbital of Ir and the electron orbital of the benzene ring in the phenyl group is improved, that is, the stability of the complex is improved. In order to obtain a highly durable compound, it is particularly preferable that R ³ is a phenyl group having an alkyl group having 5 or more carbon atoms which may have a substituent.

Further, in R ³ , it is particularly preferable that the p-position of the phenyl group is an alkyl group having 5 or more carbon atoms. By having the alkyl group at the p-position, the effect of the alkyl group as an electron-donating group is easily exhibited. As the organometallic complex of the present invention, a compound in which the p-position is an alkyl group having 5 or more carbon atoms is particularly preferable.

In addition to the phenyl skeleton of the organometallic complex of the present invention, as the ligand of the Ir complex, for example, R ⁵ and R ⁶ in the above formula (1) are bonded to form an aromatic 6-membered ring, and an isoquinoline ring A skeleton formed by forming can also be considered. However, according to the study by the present inventors, in an Ir complex having a phenylisoquinoline skeleton (ligand consisting of), the ligand has an alkyl group having 5 or more carbon atoms as in the organometallic complex of the present invention. When it has, there exists a tendency for the problem that stability falls.

  For example, in the case of a phenylisoquinoline-based Ir complex, the stability decreases when an alkyl group having a large carbon number is introduced. Specifically, in the following Piq-1 and Piq-2, when left at room temperature in a state dissolved in an organic solvent such as acetonitrile, the decomposition rate of Piq-1 is significantly higher than that of Piq-2. That is, the result that stability is low is obtained. This phenomenon is presumed to be due to the fact that the stability of the complex itself is low, whereas the energy-stabilizing effect of the complex-forming ligand is liberated from the complex and diffuses. The

Thus, simply introducing a long-chain alkyl group does not improve the stability of any metal complex, and may impair the stability in some cases. On the other hand, the compound represented by the formula (1) according to the present invention has a specific substituent, for example, preferably a phenyl group having an alkyl group having 5 or more carbon atoms, a specific position, for example, the R ³ position in the formula (1). It has been found that the solubility in the solvent, the dispersibility, and the like are improved, and the solvent is stably present in the solvent.
<Molecular weight>
The molecular weight of the organometallic complex represented by the above formula (1) of the present invention is usually 850 or more, preferably 900 or more, and usually 3000 or less, preferably 2000 or less. When the upper limit is exceeded, the stability of the complex may be remarkably deteriorated.

<Specific example>
Specific examples of the organometallic complex represented by the above formula (1) of the present invention are shown in [Chemical Formula 4] to [Chemical Formula 6], but the organometallic complex of the present invention is limited to the following examples. It is not a thing.

<Synthesis method>
As a method for synthesizing the organometallic complex represented by the above formula (1) of the present invention, the following method can be used.
For example, a ligand, a phenylquinoline derivative, can be prepared by a Suzuki coupling method such as a quinoline derivative and a phenylboronic acid derivative (Tetrahedron Letters, 36, 3437-3440, 1979), a Friedlander quinoline synthesis method. (Chem. Rev. 109, 2652-2671, 2009). Organometallic complex further in glycerol phenylquinoline derivatives, a method of heating with IrCl ₃ hydrate and 200~250 ℃ (J.Am.Chem.Soc., 107, pp. 1431 to 1432, 1985), etc. Can be synthesized. As a purification method and the like, a generally known method can be used.

More specifically, in the formula (1), R ² and R ⁶ have a substituent (R), R ³ is a phenyl group having a straight-chain alkyl group having 6 carbon atoms, R ¹ , R ⁴ , R ⁵ , and R ^{7 to} R ¹⁰ are each a hydrogen atom, and a synthetic reaction scheme of the compound is shown in [Chemical Formula 7]. In the reaction scheme, X represents a halogen atom, and acac represents acetylacetonate.

<Light emitting material>
The luminescent material of the present invention is composed of the above-described organometallic complex. The light emitting material of the present invention can be particularly suitably used as a light emitting material (phosphorescent dopant) of an organic electroluminescent element.

<Organic metal complex-containing composition>
Since the organometallic complex of the present invention is excellent in solubility, it is preferably used together with a solvent. Hereinafter, the composition (organometallic complex-containing composition) containing the organometallic complex of the present invention and a solvent will be described.

  The organometallic complex-containing composition of the present invention contains the above-described organometallic complex of the present invention and a solvent. The organometallic complex-containing composition of the present invention is usually used for forming a layer or a film by a wet film forming method, and particularly preferably used for forming an organic layer of an organic electroluminescent element. The organic layer is particularly preferably a light emitting layer.

  The content of the organometallic complex in the organometallic complex-containing composition is usually 0.1% by mass or more, preferably 1% by mass or more, and usually 99.99% by mass or less, preferably 99.9% by mass or less. It is. By setting the content of the organometallic complex in the composition within this range, holes and electrons are efficiently injected from the adjacent layer (for example, hole transport layer or hole blocking layer) to the light emitting layer, The driving voltage can be reduced. In addition, only 1 type may be contained in the organometallic complex containing composition of this invention, and the organometallic complex of this invention may be contained in combination of 2 or more type.

The solvent contained in the organometallic complex-containing composition of the present invention is a volatile liquid component used for forming a layer containing an organometallic complex by wet film formation.
The solvent is not particularly limited as long as it is a solvent in which the organometallic complex of the present invention which is a solute and a charge transporting compound described later are well dissolved, and preferred solvents include the following.

  For example, alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin, and bicyclohexane; aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene, and tetralin; halogenated fragrances such as chlorobenzene, dichlorobenzene, and trichlorobenzene Group hydrocarbons: 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethyl Aromatic ethers such as anisole and diphenyl ether; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, ethyl benzoate, propyl benzoate and n-butyl benzoate; Alicyclic ketones such as Sanone, Cyclooctanone and Fencon; Alicyclic alcohols such as cyclohexanol and cyclooctanol; Aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; Aliphatic alcohols such as butanol and hexanol; Ethylene Examples include aliphatic ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA).

Of these, alkanes and aromatic hydrocarbons are preferable.
One of these solvents may be used alone, or two or more thereof may be used in any combination and ratio.
The boiling point of the solvent is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 150 ° C. or higher, particularly preferably 200 ° C. or higher, and usually 270 ° C. or lower, preferably 250 ° C. or lower, more preferably 230 ° C. It is as follows. Below this range, film formation stability may be reduced by evaporation of the solvent from the composition during wet film formation.

  The content of the solvent is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and preferably 99.95 parts by mass or less with respect to 100 parts by mass of the composition. More preferably, it is 99.9 mass parts or less, Most preferably, it is 99.8 mass parts or less. When the content of the solvent is below this lower limit, the viscosity of the composition becomes too high, and the film forming workability may be lowered. On the other hand, if the upper limit is exceeded, the film thickness obtained by removing the solvent after film formation cannot be obtained, and thus film formation tends to be difficult.

When the organometallic complex-containing composition of the present invention is used for, for example, an organic electroluminescent element, it contains a charge transporting compound used for an organic electroluminescent element, particularly a light emitting layer, in addition to the above-described organometallic complex and solvent. be able to.
When forming the light emitting layer of the organic electroluminescent element using the organometallic complex-containing composition of the present invention, the organometallic complex of the present invention is used as a dopant material, and another charge transporting compound is contained as a host material. Is preferred.

  As other charge transporting compounds that can be contained in the organometallic complex-containing composition of the present invention, those conventionally used as materials for organic electroluminescence devices can be used. For example, pyridine, carbazole, naphthalene, perylene, pyrene, anthracene, chrysene, naphthacene, phenanthrene, coronene, fluoranthene, benzophenanthrene, fluorene, acetonaphthofluoranthene, coumarin, p-bis (2-phenylethenyl) benzene and the like Derivatives, quinacridone derivatives, DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) compounds, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, azabenzothioxanthene, aryl Examples thereof include a condensed aromatic ring compound substituted with an amino group, a styryl derivative substituted with an arylamino group, and the like.

  One of these may be used alone, or two or more may be used in any combination and ratio.

  The content of the other charge transporting compound in the organometallic complex-containing composition of the present invention is usually 1 part by mass or more and usually 50 parts by mass or less, preferably 100 parts by mass of the composition. 30 parts by mass or less.

  The content of the other charge transporting compound in the organometallic complex-containing composition is usually 50% by mass or less, preferably 30% by mass with respect to the organometallic complex of the present invention in the organometallic complex-containing composition. In addition, it is usually 0.01% by mass or more, preferably 0.1% by mass or more.

  The organometallic complex-containing composition of the present invention may further contain other compounds, if necessary, in addition to the above-mentioned compounds. For example, in addition to the above solvent, another solvent may be contained. Examples of such a solvent include amides such as N, N-dimethylformamide and N, N-dimethylacetamide, and dimethyl sulfoxide. One of these may be used alone, or two or more may be used in any combination and ratio.

  Moreover, the organometallic complex containing composition of this invention may contain various additives, such as a leveling agent and an antifoamer, for the purpose of improving film forming property.

<Application>
The organometallic complex of the present invention can be suitably used as a material used for an organic electroluminescent element, that is, an organic electroluminescent element material, and can also be suitably used as a luminescent material such as an organic electroluminescent element and other light emitting elements. It is.

<Organic electroluminescent device>
The organic electroluminescent element of the present invention is characterized in that it has an anode and an organic layer between the anode and the cathode on a substrate, and the organic layer contains the organometallic complex of the present invention. The organic layer may be any of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and the like, but the organic layer containing the organometallic complex of the present invention is a light emitting layer. Is preferred.

Below, the layer structure of the organic electroluminescent element of this invention, its general formation method, etc. are demonstrated with reference to FIG.
FIG. 1 is a schematic cross-sectional view showing a structural example of an organic electroluminescent device according to the present invention. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is a hole blocking layer, 7 is an electron transport layer, 8 is an electron injection layer, 9 represents each cathode.

  In the present invention, the wet film forming method includes, for example, spin coating method, dip coating method, die coating method, bar coating method, blade coating method, roll coating method, spray coating method, capillary coating method, ink jet method, screen printing. This method is a wet film formation method such as a method, a gravure printing method, or a flexographic printing method. Among these film forming methods, a spin coating method, a spray coating method, and an ink jet method are preferable. This is because the liquid property specific to the coating composition used in the organic electroluminescence device is matched.

(substrate)
The substrate 1 serves as a support for the organic electroluminescent element, and a quartz or glass plate, a metal plate or a metal foil, a plastic film, a sheet, or the like is used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, polysulfone or the like is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too small, the organic electroluminescent element may be deteriorated by the outside air that has passed through the substrate. For this reason, a method of providing a gas barrier property by providing a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate is also a preferable method.

(anode)
The anode 2 serves to inject holes into the layer on the light emitting layer side.
This anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, carbon black, or It is composed of a conductive polymer such as poly (3-methylthiophene), polypyrrole, or polyaniline.

  In general, the anode 2 is often formed by a sputtering method, a vacuum deposition method, or the like. In addition, when forming the anode 2 using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and conductive polymer fine powder, an appropriate binder resin solution It is also possible to form the anode 2 by dispersing it and applying it onto the substrate 1. Furthermore, in the case of a conductive polymer, a thin film can be directly formed on the substrate 1 by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate 1 (Appl. Phys. Lett. 60, 2711, 1992).

The anode 2 usually has a single-layer structure, but it can also have a laminated structure made of a plurality of materials if desired.
The thickness of the anode 2 varies depending on the required transparency. When transparency is required, the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably about 500 nm or less. When it may be opaque, the thickness of the anode 2 is arbitrary, and the anode 2 may be the same as the substrate 1. Furthermore, it is also possible to laminate different conductive materials on the anode 2 described above.

  For the purpose of removing impurities adhering to the anode 2 and adjusting the ionization potential to improve the hole injection property, the surface of the anode 2 is treated with ultraviolet (UV) / ozone, or with oxygen plasma or argon plasma. It is preferable to do.

(Hole injection layer)
The hole injection layer 3 is a layer that transports holes from the anode 2 to the light emitting layer 5, and is usually formed on the anode 2.

The method for forming the hole injection layer 3 according to the present invention may be a vacuum deposition method or a wet film formation method, and is not particularly limited, but the hole injection layer 3 is formed by a wet film formation method from the viewpoint of reducing dark spots. It is preferable.
The thickness of the hole injection layer 3 is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less.

<Formation of hole injection layer by wet film formation method>
When forming the hole injection layer 3 by wet film formation, the material for forming the hole injection layer 3 is usually mixed with an appropriate solvent (hole injection layer solvent) to form a film-forming composition (positive A composition for forming a hole injection layer), and applying the composition for forming a hole injection layer on a layer (usually an anode) corresponding to the lower layer of the hole injection layer 3 by an appropriate technique. The hole injection layer 3 is formed by coating and drying.

(Hole transporting compound)
The composition for forming a hole injection layer usually contains a hole transporting compound and a solvent as a constituent material of the hole injection layer.
The hole transporting compound is a compound having a hole transporting property that is usually used in a hole injection layer of an organic electroluminescence device, and may be a polymer compound or the like, a monomer or the like. Although it may be a low molecular compound, it is preferably a high molecular compound.

  The hole transporting compound is preferably a compound having an ionization potential of 4.5 eV to 6.0 eV from the viewpoint of a charge injection barrier from the anode 2 to the hole injection layer 3. Examples of hole transporting compounds include aromatic amine derivatives, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives, polythiophene derivatives, benzylphenyl derivatives, compounds in which tertiary amines are linked by a fluorene group, hydrazone derivatives, silazane derivatives, silanamines Derivatives, phosphamine derivatives, quinacridone derivatives, polyaniline derivatives, polypyrrole derivatives, polyphenylene vinylene derivatives, polythienylene vinylene derivatives, polyquinoline derivatives, polyquinoxaline derivatives, carbon and the like.

  In the present invention, the derivative includes, for example, an aromatic amine derivative, and includes an aromatic amine itself and a compound having an aromatic amine as a main skeleton. It may be a mer.

  The hole transporting compound used as the material for the hole injection layer 3 may contain any one of these compounds alone, or may contain two or more. When two or more hole transporting compounds are contained, the combination thereof is arbitrary, but one or more aromatic tertiary amine polymer compounds and one or two other hole transporting compounds are used. It is preferable to use the above in combination.

  Among the above examples, an aromatic amine compound is preferable from the viewpoint of amorphousness and visible light transmittance, and an aromatic tertiary amine compound is particularly preferable. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.

  The type of the aromatic tertiary amine compound is not particularly limited, but from the viewpoint of uniform light emission due to the surface smoothing effect, a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (a polymerizable compound in which repeating units are linked) is further included. preferable. Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following formula (I).

(In Formula (I), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar ^{3 to} Ar ⁵ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Represents a linking group selected from the group of linking groups, and two groups bonded to the same N atom among Ar ^{1 to} Ar ⁵ may be bonded to each other to form a ring.

(In said each formula, Ar < ⁶ > -Ar < ¹⁶ > represents each independently the aromatic hydrocarbon group which may have a substituent, or the aromatic heterocyclic group which may have a substituent. R ³¹ and R ³² each independently represent a hydrogen atom or an arbitrary substituent.)

As the aromatic hydrocarbon group and the aromatic heterocyclic group of Ar ^{1 to} Ar ¹⁶ , a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene from the viewpoint of the solubility, heat resistance, hole injection / transport property of the polymer compound A group derived from a ring or a pyridine ring is preferred, and a group derived from a benzene ring or a naphthalene ring is more preferred.

The aromatic hydrocarbon group and aromatic heterocyclic group of Ar ^{1 to} Ar ¹⁶ may further have a substituent. The molecular weight of the substituent is usually 400 or less, preferably about 250 or less. As the substituent, an alkyl group, an alkenyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group and the like are preferable.
When R ³¹ and R ³² are optional substituents, examples of the substituent include alkyl groups, alkenyl groups, alkoxy groups, silyl groups, siloxy groups, aromatic hydrocarbon groups, aromatic heterocyclic groups, and the like. .

Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the formula (I) include those described in International Publication No. 2005/089024.
In addition, as a hole transporting compound, a conductive polymer (PEDOT / PSS) obtained by polymerizing 3,4-ethylenedioxythiophene, which is a derivative of polythiophene, in high molecular weight polystyrene sulfonic acid. Is also preferred. Moreover, the end of this polymer may be capped with methacrylate or the like.

  The concentration of the hole transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.01% by mass or more, preferably in terms of film thickness uniformity. Is 0.1% by mass or more, more preferably 0.5% by mass or more, and is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less. If this concentration is too high, film thickness unevenness may occur, and if it is too low, defects may occur in the formed hole injection layer.

(Electron-accepting compound)
The composition for forming a hole injection layer preferably contains an electron accepting compound as a constituent material of the hole injection layer. Here, the electron-accepting compound is preferably a compound having an oxidizing power and the ability to accept one electron from the above-described hole-transporting compound, and specifically, a compound having an electron affinity of 4 eV or more is preferable. A compound that is a compound of 5 eV or more is more preferable.

  Examples of such electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. Examples thereof include one or more compounds selected from the group. More specifically, an onium salt substituted with an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and triphenylsulfonium tetrafluoroborate (International Publication No. WO 2005/089024); High valent inorganic compounds such as iron (III) chloride (Japanese Patent Laid-Open No. 11-251067), ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene, tris (pendafluorophenyl) borane (Japanese Patent Laid-Open No. 2003-31365) Aromatic boron compounds such as); fullerene derivatives; iodine; sulfonate ions such as polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and the like.

These electron accepting compounds can improve the conductivity of the hole injection layer by oxidizing the hole transporting compound.
The content of the electron-accepting compound in the hole-injecting layer or the composition for forming a hole-injecting layer with respect to the hole-transporting compound is usually 0.1 mol% or more, preferably 1 mol% or more, and usually It is 100 mol% or less, preferably 40 mol% or less.

(Other components)
As a material for the hole injection layer, other components may be further contained in addition to the above-described hole transporting compound and electron accepting compound as long as the effects of the present invention are not significantly impaired. Examples of other components include various light emitting materials, electron transporting compounds, binder resins, and coating property improving agents. In addition, only 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and a ratio.

(solvent)
At least one of the solvents of the composition for forming a hole injection layer used in the wet film formation method is preferably a compound that can dissolve the constituent material of the hole injection layer. The boiling point of this solvent is usually 110 ° C. or higher, preferably 140 ° C. or higher, more preferably 200 ° C. or higher, and usually 400 ° C. or lower, preferably 300 ° C. or lower. If the boiling point of the solvent is too low, the drying speed is too high and the film quality may be deteriorated. Further, if the boiling point of the solvent is too high, it is necessary to increase the temperature of the drying process, and there is a possibility of adversely affecting other layers and the substrate.

Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like.
Examples of ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole , Aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole.

Examples of the ester solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
Examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, 3-isopropylpropylphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, and methylnaphthalene. Can be mentioned.

Examples of the amide solvent include N, N-dimethylformamide and N, N-dimethylacetamide.
In addition, dimethyl sulfoxide and the like can also be used.
These solvent may use only 1 type and may use 2 or more types by arbitrary combinations and a ratio.

(Film formation method)
After preparing the composition for forming the hole injection layer, the composition is applied on the layer corresponding to the lower layer of the hole injection layer 3 (usually the anode 2) by wet film formation, and dried. The hole injection layer 3 is formed.

The temperature in the film forming step is preferably 10 ° C. or higher, and preferably 50 ° C. or lower in order to prevent film loss due to the formation of crystals in the composition.
Although the relative humidity in a film-forming process is not limited unless the effect of this invention is impaired remarkably, it is 0.01 ppm or more normally and 80% or less normally.
After the film formation, the film of the composition for forming a hole injection layer is usually dried by heating or the like. Examples of the heating means used in the heating step include a clean oven, a hot plate, infrared rays, a halogen heater, microwave irradiation and the like. Among them, a clean oven and a hot plate are preferable in order to uniformly apply heat to the entire film.

  The heating temperature in the heating step is preferably heated at a temperature equal to or higher than the boiling point of the solvent used in the composition for forming a hole injection layer as long as the effects of the present invention are not significantly impaired. In the case of a mixed solvent containing two or more types of solvents used in the hole injection layer, at least one type is preferably heated at a temperature equal to or higher than the boiling point of the solvent. In consideration of an increase in the boiling point of the solvent, the heating step is preferably performed at 120 ° C. or higher, preferably 410 ° C. or lower.

  In the heating step, the heating time is not limited as long as the heating temperature is not lower than the boiling point of the solvent of the composition for forming a hole injection layer and sufficient insolubilization of the coating film does not occur. Is less than a minute. If the heating time is too long, the components of the other layers tend to diffuse, and if it is too short, the hole injection layer tends to be inhomogeneous. Heating may be performed in two steps.

<Formation of hole injection layer by vacuum deposition>
When the hole injection layer 3 is formed by vacuum deposition, one or more of the constituent materials of the hole injection layer 3 (the aforementioned hole transporting compound, electron accepting compound, etc.) are placed in a vacuum container. Put in crucibles installed (in case of using two or more materials, put them in each crucible), evacuate the inside of the vacuum vessel to about 10 ⁻⁴ Pa with a suitable vacuum pump, and then heat the crucible (two types When using the above materials, heat each crucible) and evaporate by controlling the amount of evaporation (when using two or more materials, evaporate by independently controlling the amount of evaporation) and face the crucible Then, the hole injection layer 3 is formed on the anode 2 of the substrate placed on the substrate. In addition, when using 2 or more types of materials, the hole injection layer 3 can also be formed by putting those mixtures into a crucible, heating and evaporating.

The degree of vacuum at the time of vapor deposition is not limited as long as the effects of the present invention are not significantly impaired, but usually 0.1 × 10 ⁻⁶ Torr (0.13 × 10 ⁻⁴ Pa) or more, usually 9.0 × 10 ⁻⁶ Torr. (12.0 × 10 ⁻⁴ Pa) or less. The deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 Å / second or more and usually 5.0 Å / second or less. The film forming temperature at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is preferably 10 ° C. or higher, preferably 50 ° C. or lower.

(Hole transport layer)
The method for forming the hole transport layer 4 according to the present invention may be a vacuum deposition method or a wet film formation method, and is not particularly limited, but the hole transport layer 4 is formed by a wet film formation method from the viewpoint of reducing dark spots. It is preferable.
The hole transport layer 4 can be formed on the hole injection layer 3 when there is a hole injection layer and on the anode 2 when there is no hole injection layer 3. The organic electroluminescent device of the present invention may have a configuration in which the hole transport layer is omitted.

  The material for forming the hole transport layer 4 is preferably a material having high hole transportability and capable of efficiently transporting injected holes. Therefore, it is preferable that the ionization potential is small, the transparency to visible light is high, the hole mobility is large, the stability is high, and impurities that become traps are not easily generated during manufacturing or use. In many cases, it is preferable not to quench the light emitted from the light emitting layer 5 or to form an exciplex with the light emitting layer 5 to reduce the efficiency because it is in contact with the light emitting layer 5.

  Such a material for the hole transport layer 4 may be any material conventionally used as a constituent material for the hole transport layer. For example, the hole transport property used for the hole injection layer 3 described above. What was illustrated as a compound is mentioned. In addition, arylamine derivatives, fluorene derivatives, spiro derivatives, carbazole derivatives, pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, phthalocyanine derivatives, porphyrin derivatives, silole derivatives, oligothiophene derivatives, condensed polycyclic aromatics Group derivatives, metal complexes and the like.

  In addition, for example, polyvinylcarbazole derivatives, polyarylamine derivatives, polyvinyltriphenylamine derivatives, polyfluorene derivatives, polyarylene derivatives, polyarylene ether sulfone derivatives containing tetraphenylbenzidine, polyarylene vinylene derivatives, polysiloxane derivatives, polythiophenes Derivatives, poly (p-phenylene vinylene) derivatives, and the like. These may be any of an alternating copolymer, a random polymer, a block polymer, or a graft copolymer. Further, it may be a polymer having a branched main chain and three or more terminal portions, or a so-called dendrimer.

Of these, polyarylamine derivatives and polyarylene derivatives are preferred.
The polyarylamine derivative is preferably a polymer containing a repeating unit represented by the following formula (II). In particular, a polymer composed of a repeating unit represented by the following formula (II) is preferable. In this case, Ar ^a or Ar ^b may be different in each repeating unit.

(In formula (II), Ar ^a and Ar ^b each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.)

  Examples of the aromatic hydrocarbon group which may have a substituent include, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, and acenaphthene. Examples thereof include a group derived from a 6-membered monocyclic ring or a 2-5 condensed ring, such as a ring, a fluoranthene ring, and a fluorene ring, and a group in which two or more of these rings are linked by a direct bond.

  Examples of the aromatic heterocyclic group which may have a substituent include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring. , Pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine Ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Or a group and the rings of from 2-4 fused rings include groups formed by connecting a direct bond or two or more rings.

From the viewpoints of solubility and heat resistance, Ar ^a and Ar ^b are each independently selected from the group consisting of a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, pyrene ring, thiophene ring, pyridine ring, and fluorene ring. A group derived from a selected ring or a group formed by linking two or more benzene rings (for example, a biphenyl group or a terphenyl group) is preferable. Among these, a group derived from a benzene ring (phenyl group), a group formed by connecting two benzene rings (biphenyl group), and a group derived from a fluorene ring (fluorenyl group) are preferable.

Examples of the substituent that the aromatic hydrocarbon group and the aromatic heterocyclic group in Ar ^a and Ar ^b may have include an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, and a dialkyl. Examples thereof include an amino group, a diarylamino group, an acyl group, a halogen atom, a haloalkyl group, an alkylthio group, an arylthio group, a silyl group, a siloxy group, a cyano group, an aromatic hydrocarbon ring group, and an aromatic heterocyclic group.

As the polyarylene derivative, an arylene group such as an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent exemplified as Ar ^a or Ar ^b in the formula (II) is used as its repeating unit. The polymer which has is mentioned.
As the polyarylene derivative, a polymer having a repeating unit composed of the following formula (III-1) and / or the following formula (III-2) is preferable.

(In formula (III-1), R ^a , R ^b , R ^c and R ^d are each independently an alkyl group, an alkoxy group, a phenylalkyl group, a phenylalkoxy group, a phenyl group, a phenoxy group, an alkylphenyl group, Represents an alkoxyphenyl group, an alkylcarbonyl group, an alkoxycarbonyl group, or a carboxy group, and t and s each independently represent an integer of 0 to 3. When t or s is 2 or more, a plurality of molecules included in one molecule R ^a or R ^b may be the same or different, and adjacent R ^a or R ^b may form a ring.)

(In the formula (III-2), R ^e and R ^f are independently the same as R ^a , R ^b , R ^c or R ^d in the formula (III-1). Independently, it represents an integer of 0 to 3. When r or u is 2 or more, a plurality of R ^e and R ^f contained in one molecule may be the same or different, and adjacent R ^e or R ^f may form a ring, and X represents an atom or a group of atoms constituting a 5-membered ring or a 6-membered ring.)

  Specific examples of X include an oxygen atom, a boron atom which may have a substituent, a nitrogen atom which may have a substituent, a silicon atom which may have a substituent, and a substituent. A phosphorus atom which may be substituted, a sulfur atom which may have a substituent, a carbon atom which may have a substituent, or a group formed by bonding these.

  Further, the polyarylene derivative has a repeating unit represented by the following formula (III-3) in addition to the repeating unit consisting of the above formula (III-1) and / or the above formula (III-2). Is preferred.

(In formula (III-3), Ar ^{c to} Ar ^j each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent. Independently represents 0 or 1.)

Specific examples of Ar ^{c to} Ar ^j are the same as Ar ^a and Ar ^b in the formula (II).

  Specific examples of the above formulas (III-1) to (III-3) and specific examples of polyarylene derivatives include those described in JP-A-2008-98619.

In the case of forming the hole transport layer 4 by a wet film formation method, a composition for forming a hole transport layer is prepared in the same manner as the formation of the hole injection layer 3 and then heated and dried after the wet film formation. .
The composition for forming a hole transport layer contains a solvent in addition to the above hole transport compound. The solvent used is the same as that used for the composition for forming a hole injection layer. The film forming conditions, heat drying conditions, and the like are the same as in the case of forming the hole injection layer 3.

In the case where the hole transport layer is formed by the vacuum deposition method, the film forming conditions are the same as those in the case of forming the hole injection layer 3.
The hole transport layer 4 may contain various light emitting materials, electron transport compounds, binder resins, coating property improving agents, and the like in addition to the hole transport compound.
The hole transport layer 4 may be a layer formed by crosslinking a crosslinkable compound. The crosslinkable compound is a compound having a crosslinkable group, and forms a network polymer compound by crosslinking.

Examples of this crosslinkable group include groups derived from cyclic ethers such as oxetane and epoxy; groups derived from unsaturated double bonds such as vinyl, trifluorovinyl, styryl, acrylic, methacryloyl and cinnamoyl; benzo Examples include groups derived from cyclobutene.
The crosslinkable compound may be any of a monomer, an oligomer, and a polymer. The crosslinkable compound may have only 1 type, and may have 2 or more types by arbitrary combinations and ratios.

  As the crosslinkable compound, a hole transporting compound having a crosslinkable group is preferably used. Examples of the hole transporting compound include those exemplified above, and those having a crosslinkable group bonded to the main chain or side chain with respect to these hole transporting compounds. In particular, the crosslinkable group is preferably bonded to the main chain via a linking group such as an alkylene group. In particular, the hole transporting compound is preferably a polymer containing a repeating unit having a crosslinkable group, and the above formula (II) and formulas (III-1) to (III-3) can be used as a crosslinkable group. Is preferably a polymer having a repeating unit bonded directly or via a linking group.

  As the crosslinkable compound, a hole transporting compound having a crosslinkable group is preferably used. Examples of hole transporting compounds include nitrogen-containing aromatic compound derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, carbazole derivatives, phthalocyanine derivatives, porphyrin derivatives; triphenylamine derivatives Silole derivatives; oligothiophene derivatives, condensed polycyclic aromatic derivatives, metal complexes and the like. Among them, nitrogen-containing aromatic derivatives such as pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, carbazole derivatives; triphenylamine derivatives, silole derivatives, condensed polycyclic aromatic derivatives, metal complexes, etc. Particularly preferred are triphenylamine derivatives.

In order to form the hole transport layer 4 by crosslinking the crosslinkable compound, a composition for forming a hole transport layer in which the crosslinkable compound is dissolved or dispersed in a solvent is usually prepared and deposited by wet film formation. To crosslink.
The composition for forming a hole transport layer may contain an additive for promoting a crosslinking reaction in addition to the crosslinking compound. Examples of additives that accelerate the crosslinking reaction include polymerization initiators and polymerization accelerators such as alkylphenone compounds, acylphosphine oxide compounds, metallocene compounds, oxime ester compounds, azo compounds, onium salts; condensed polycyclic hydrocarbons, Examples thereof include photosensitizers such as porphyrin compounds and diaryl ketone compounds.

Further, it may contain a coating property improving agent such as a leveling agent and an antifoaming agent; an electron accepting compound; a binder resin and the like.
In the composition for forming a hole transport layer, the crosslinkable compound is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and usually 50% by mass or less. , Preferably it is 20 mass% or less, More preferably, it contains 10 mass% or less.

After forming a composition for forming a hole transport layer containing a crosslinkable compound at such a concentration on the lower layer (usually the hole injection layer 3), the composition is crosslinked by heating and / or irradiation with electromagnetic energy such as light. Are crosslinked to form a network polymer compound.
Conditions such as temperature and humidity during film formation are the same as those during the wet film formation of the hole injection layer 3.
The heating method after film formation is not particularly limited. As heating temperature conditions, it is 120 degreeC or more normally, Preferably it is 400 degrees C or less.

  The heating time is usually 1 minute or longer, preferably 24 hours or shorter. The heating means is not particularly limited, and means such as placing a laminated body having a deposited layer on a hot plate or heating in an oven is used. For example, conditions such as heating on a hot plate at 120 ° C. or more for 1 minute or more can be used.

In the case of irradiation with electromagnetic energy such as light, a method of irradiating directly using an ultraviolet / visible / infrared light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a halogen lamp, an infrared lamp, etc. Examples include a mask aligner and a method of irradiation using a conveyor type light irradiation device. In electromagnetic energy irradiation other than light, for example, there is a method of irradiation using a device that irradiates a microwave generated by a magnetron, a so-called microwave oven.
As the irradiation time, it is preferable to set conditions necessary for reducing the solubility of the film, but irradiation is usually performed for 0.1 seconds or longer, preferably 10 hours or shorter.

Heating and irradiation of electromagnetic energy such as light may be performed individually or in combination. When combined, the order of implementation is not particularly limited.
The film thickness of the hole transport layer 4 thus formed is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less.

(Light emitting layer)
When the hole injection layer 3 or the hole transport layer 4 is provided, the light emitting layer 5 is provided on the hole transport layer 4. The light emitting layer 5 is a layer that is excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 between electrodes to which an electric field is applied, and becomes a main light emitting source.

<Light emitting layer material>
The light emitting layer 5 contains at least a material having a light emitting property (light emitting material) as a constituent material, and preferably a compound having a hole transporting property (hole transporting compound) or an electron transport. A compound (electron transporting compound) having the following properties: A light emitting material may be used as a dopant material, and a hole transporting compound, an electron transporting compound, or the like may be used as a host material. There is no particular limitation on the light-emitting material, and a material that emits light at a desired light emission wavelength and has high light emission efficiency may be used. However, the organometallic complex of the present invention is preferably used.

In particular, in the organic electroluminescent element of the present invention, the light emitting layer is preferably formed by a wet film forming method using the organometallic complex-containing composition of the present invention.
Furthermore, the light emitting layer 5 may contain other components as long as the effects of the present invention are not significantly impaired. In addition, when forming the light emitting layer 5 with a wet film-forming method, it is preferable to use a low molecular weight material (molecular weight is usually 10,000 or less, preferably 5000 or less).

<Formation of light emitting layer>
When forming the light emitting layer 5 by a wet film-forming method, the material used for the light emitting layer is dissolved in an appropriate solvent to form a composition for forming a light emitting layer (in the case of containing the organometallic complex of the present invention, an organometallic complex-containing composition). ) Is prepared, and a film is formed using it.
The solvent for the light emitting layer to be contained in the composition for forming the light emitting layer for forming the light emitting layer 5 by a wet film forming method is the same as that described as the solvent contained in the composition containing an organometallic complex of the present invention. It is.

  Further, the solid content concentration of the light emitting material, the charge transporting compound and the like in the composition for forming a light emitting layer is usually 0.01% by mass or more and usually 70% by mass or less. If this concentration is too large, film thickness unevenness may occur, and if it is too small, defects may occur in the film.

  After wet-deposition of the composition for forming a light emitting layer, the resulting coating film is dried and the solvent is removed to form a light emitting layer. Specifically, it is the same as the method described in the formation of the hole injection layer. The method of the wet film forming method is not limited as long as the effect of the present invention is not significantly impaired, and any of the methods described above can be used.

  The thickness of the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 3 nm or more, preferably 5 nm or more, and usually 200 nm or less, preferably 100 nm or less. If the thickness of the light emitting layer 5 is too thin, defects may occur in the film, and if it is too thick, the driving voltage may increase.

(Hole blocking layer)
A hole blocking layer 6 may be provided between the light emitting layer 5 and an electron injection layer 8 described later. The hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.

The hole blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light emitting layer 5. Have
The physical properties required for the material constituting the hole blocking layer 6 include high electron mobility, low hole mobility, a large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). Is high.

  Examples of the material for the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum, and the like. Mixed metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, distyrylbiphenyl derivatives, etc. Triazole derivatives such as styryl compounds (JP-A-11-242996), 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole (JP-A-7 -41759), phenanthroline derivatives such as bathocuproine (JP-A-10-79297), and the like. That. Further, a compound having at least one pyridine ring substituted at the 2,4,6-positions described in International Publication No. 2005/022962 is also preferable as the material of the hole blocking layer 6.

In addition, the material of the hole-blocking layer 6 may use only 1 type, and may use 2 or more types together by arbitrary combinations and ratios.
There is no restriction | limiting in the formation method of the hole-blocking layer 6. FIG. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.

The thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. is there.
Further, a hole relaxation layer may be provided instead of the hole blocking layer.

(Electron transport layer)
An electron transport layer 7 may be provided between the light emitting layer 5 and an electron injection layer 8 described later.
The electron transport layer 7 is provided for the purpose of further improving the light emission efficiency of the device, and efficiently transports electrons injected from the cathode 9 between the electrodes to which an electric field is applied in the direction of the light emitting layer 5. Formed from a compound capable of

  As an electron transport compound used for the electron transport layer 7, usually, the electron injection efficiency from the cathode 9 or the electron injection layer 8 is high, and the injected electrons are transported efficiently with high electron mobility. The compound which can be used is used. Examples of the compound satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole derivatives , Distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compounds ( JP-A-6-207169), phenanthroline derivative (JP-A-5-331459), 2-t-butyl-9,10-N, N'-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide , N-type zinc sulfide, n-type zinc Such as emissions of zinc, and the like.

In addition, the material of the electron carrying layer 7 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
There is no restriction | limiting in the formation method of the electron carrying layer 7. FIG. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.
The film thickness of the electron transport layer 7 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.

(Electron injection layer)
The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the light emitting layer 5. In order to perform electron injection efficiently, the material for forming the electron injection layer 8 is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium. Examples include lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), lithium oxide (Li ₂ O), cesium carbonate (II) (CsCO ₃ ), and the like (Applied Physics Letters, 1997, 70, 152). JP-A-10-74586; see IEEE Transactions on Electron Devices, 1997, 44, 1245; SID 04 Digest, page 154, etc.).
The film thickness is usually preferably from 0.1 nm to 5 nm.

  Furthermore, an organic electron transport compound represented by a metal complex such as a nitrogen-containing heterocyclic compound such as bathophenanthroline or an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium, or rubidium ( JP-A-10-270171, JP-A-2002-1000047, JP-A-2002-1000048, etc.) are preferable because it is possible to improve electron injection / transport properties and achieve excellent film quality. . The film thickness in this case is usually 5 nm or more, preferably 10 nm or more, and is usually 200 nm or less, preferably 100 nm or less.

In addition, the material of the electron injection layer 8 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
There is no restriction | limiting in the formation method of the electron injection layer 8. FIG. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.

(cathode)
The cathode 9 plays a role of injecting electrons into a layer (such as the electron injection layer 8 or the light emitting layer 5) on the light emitting layer 5 side.

  As the material of the cathode 9, the material used for the anode 2 can be used. However, in order to perform electron injection efficiently, a metal having a low work function is preferable. For example, tin, magnesium, indium, A suitable metal such as calcium, aluminum, silver, or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.

In addition, the material of the cathode 9 may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
The film thickness of the cathode 9 is usually the same as that of the anode 2.
Further, for the purpose of protecting the cathode 9 made of a low work function metal, it is preferable to further stack a metal layer having a high work function and stable to the atmosphere because the stability of the device is increased. For this purpose, for example, metals such as aluminum, silver, copper, nickel, chromium, gold and platinum are used. In addition, these materials may be used only by 1 type and may use 2 or more types together by arbitrary combinations and a ratio.

(Other layers)
The organic electroluminescent element according to the present invention may have another configuration without departing from the gist thereof. For example, as long as the performance is not impaired, an arbitrary layer may be provided between the anode 2 and the cathode 9 in addition to the layers described above, and an arbitrary layer may be omitted. .

(Electron blocking layer)
Examples of the optional layer include an electron blocking layer. The electron blocking layer is provided between the hole injection layer 3 or the hole transport layer 4 and the light emitting layer 5 and prevents electrons moving from the light emitting layer 5 from reaching the hole injection layer 3. Thus, the probability of recombination of holes and electrons in the light emitting layer 5 is increased, the excitons generated are confined in the light emitting layer 5, and the holes injected from the hole injection layer 3 are efficiently collected. There is a role to transport in the direction of. In particular, when a phosphorescent material or a blue light emitting material is used as the light emitting material, it is effective to provide an electron blocking layer.

  The characteristics required for the electron blocking layer include high hole transportability, a large energy gap (difference between HOMO and LUMO), and a high excited triplet level (T1). Furthermore, when the light emitting layer 5 is produced by a wet film formation method, the electron blocking layer is also required to be compatible with the wet film formation. Examples of the material used for such an electron blocking layer include a copolymer of dioctylfluorene and triphenylamine typified by F8-TFB (International Publication No. 2004/084260).

In addition, the material of an electron blocking layer may use only 1 type, and may use 2 or more types together by arbitrary combinations and a ratio.
There is no restriction | limiting in the formation method of an electron blocking layer. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.

  Moreover, in the layer structure demonstrated above, it is also possible to laminate | stack components other than a board | substrate in reverse order. For example, in the case of the layer configuration of FIG. 1, the other components on the substrate 1 are the cathode 9, the electron injection layer 8, the electron transport layer 7, the hole blocking layer 6, the light emitting layer 5, the hole transport layer 4, the positive layer. The hole injection layer 3 and the anode 2 may be provided in this order.

  Furthermore, it is also possible to constitute the organic electroluminescent element according to the present invention by laminating components other than the substrate between two substrates, at least one of which is transparent.

In addition, a structure in which a plurality of components (light emitting units) other than the substrate are stacked in a plurality of layers (a structure in which a plurality of light emitting units are stacked) may be employed. In that case, instead of the interface layer between the steps (between the light emitting units) (when the anode is ITO and the cathode is Al, these two layers), for example, a charge made of vanadium pentoxide (V ₂ O ₅ ) or the like. When a generation layer (Carrier Generation Layer: CGL) is provided, a barrier between steps is reduced, which is more preferable from the viewpoint of light emission efficiency and driving voltage.

Furthermore, the organic electroluminescent device according to the present invention may be configured as a single organic electroluminescent device, or may be applied to a configuration in which a plurality of organic electroluminescent devices are arranged in an array. You may apply to the structure by which the cathode is arrange | positioned at XY matrix form.
Each layer described above may contain components other than those described as materials unless the effects of the present invention are significantly impaired.

  The organic electroluminescent element of the present invention is used for organic EL displays and organic EL lighting. The organic electroluminescent device obtained by the present invention is described in, for example, “Organic EL Display” (Ohm, August 20, 2004, written by Shizushi Tokito, Chiba Adachi, and Hideyuki Murata). An organic EL display and organic EL illumination can be formed by the method.

  Examples The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of the following examples unless it exceeds the gist.

Example 1: Synthesis of Compound 1 (Organic Metal Complex 1 of the Present Invention) As shown in the following (1) to (6), Compound 1 (organometallic complex 1) was prepared according to the reaction schemes shown in [Chemical Formula 14] to [Chemical Formula 19]. Synthesized.

(1) Synthesis of Compound 2 To a mixture of 3-bromophenylboronic acid (25.0 g, 124.4 mmol), 1-chloroquinoline (20.3 g, 124.4 mmol) and toluene (250 ml), sodium carbonate (43.5 g) , 410.7 mmol) and nitrogen bubbling was performed for 30 minutes with stirring. Tetrakis (triphenylphosphine) palladium (4.31 g, 3.73 mmol) was added thereto, and the mixture was stirred at 130 ° C. for 3.5 hours. After confirming the disappearance of the raw material by TLC, extraction was performed twice with toluene, and the organic layer was washed once with saturated brine and concentrated under reduced pressure. The product was purified by silica gel column chromatography to obtain compound 2 (28.39 g, yield 80%).

(2) Synthesis of Compound 3 Under a nitrogen stream, n-butyllithium (1.67M) (131 ml, 217.7 mmol) was added to a tetrahydrofuran (300 ml) solution of bromohexylbenzene (50.0 g, 207.3 mmol) at −75 ° C. ) Was added dropwise and reacted for 2 hours, and further trimethoxyborane (64.6 g, 622.0 mmol) was added dropwise and stirred for 2 hours. Thereafter, 300 ml of dilute hydrochloric acid (1N) was added dropwise and stirred for 30 min, followed by extraction with ethyl acetate. The organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. Compound 3 (42.5 g, 99% yield) was obtained as a colorless solid.

(3) Synthesis of Compound 4 Under a nitrogen stream, Compound 2 (13.5 g, 47.5 mmol) and Compound 3 (10.8 g, 52.8 mmol) were added to toluene (240 ml), ethanol (120 ml), water (120 ml). ), Tripotassium phosphate (33.5 g, 158 mmol) was added, and nitrogen bubbling was performed for 30 minutes with stirring. Tetrakis (triphenylphosphine) palladium (2.5 g, 2.18 mmol) was added thereto and stirred at 130 ° C. for 3.5 hours. After confirming the disappearance of the raw material by TLC, extraction was performed twice with toluene, and the organic layer was washed once with saturated brine and concentrated under reduced pressure. The product was purified by silica gel column chromatography to obtain compound 4 (17.2 g, yield 98%).

(4) Synthesis of Compound 5 Under a nitrogen stream, compound 4 (13.5 g, 36.9 mmol), iridium chloride n-hydrate (6.85 g, 18.5 mmol), 2-ethoxyethanol (200 ml), water (66 ml) was added and stirred at 135 ° C. for 10 hours. Thereafter, extraction with dichloromethane was performed, and the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. Compound 5 (11.9 g, 66% yield) was obtained as a red solid.

(5) Synthesis of Compound 6 Under a nitrogen stream, 2-ethoxyethanol (100 ml) was added to Compound 5 (11.9 g, 6.22 mmol) and sodium acetylacetonate (3.80 g, 31.0 mmol). Stir at 9 ° C. for 9 hours. Thereafter, extraction with dichloromethane was performed, and the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in dichloromethane and purified with basic silica gel to remove the origin component. Compound 6 (7.75 g, 61% yield) was obtained as a red solid.

(6) Synthesis of Compound 1 Glycerol (230 ml) was added to Compound 6 (7.0 g, 3.56 mmol) and Compound 4 (13.6 g, 37.2 mmol) under a nitrogen stream and stirred at 190 ° C. for 17 hours. . Thereafter, extraction with dichloromethane was performed, and the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in dichloromethane and purified with basic silica gel to remove the origin component. After purification with basic silica gel again, the product was dissolved in toluene, suspended and washed with methanol, and the precipitate was collected by suction filtration. Compound 1 (2.93 g, 69% yield) was obtained as a red solid.

¹ H-NMR δ [ppm]; 8.18 (d, 3H), 8.09 (d, 3H), 8.07 (d, 3H), 7.97 (s, 3H) 7.67 (d, 3H) ), 7.47 (d, 6H), 7.20 (t, 3H), 7.16 (d, 6H), 6.96 (d, 3H), 6.72 (t, 3H), 6.61 (D, 3H), 2.59 (t, 6H), 1.30 (m, 24H), 0.89 (t, 9H)

Example 2: Synthesis of Compound 9 (Comparative Organometallic Complex 9) As shown in (1) to (3) below, Compound 9 (organometallic complex 9) was prepared according to the reaction scheme shown in [Chemical Formula 20] to [Chemical Formula 22]. Synthesized.

(1) Synthesis of Compound 7 Under a nitrogen stream, phenylquinoline (9.4 g, 45.8 mmol), iridium chloride n-hydrate (8.59 g, 22.9 mmol), 2-ethoxyethanol (130 ml), water (42 ml) was added and stirred at 135 ° C. for 10 hours. Thereafter, extraction with dichloromethane was performed, and the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. Compound 7 (1.78 g, yield 12%) was obtained as a red solid.

(2) Synthesis of Compound 8 Under a nitrogen stream, 2-ethoxyethanol (280 ml) was added to Compound 7 (1.27 g, 1 mmol) and sodium acetylacetonate (2.0 g, 20 mmol) at 135 ° C. for 4 hours. Stir. Thereafter, extraction with dichloromethane was performed, and the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in dichloromethane and purified with basic silica gel to remove the origin component. Compound 8 (545 mg, 39% yield) was obtained as a red solid.

(3) Synthesis of Compound 9 Glycerol (7.35 ml) was added to Compound 8 (245 mg, 0.35 mmol) and phenylquinoline (0.36 g, 1.75 mmol) under a nitrogen stream and stirred at 190 ° C. for 17 hours. . Thereafter, extraction with dichloromethane was performed, and the organic layer was washed with saturated brine, dried over sodium sulfate, and concentrated under reduced pressure. The residue was dissolved in dichloromethane and purified with basic silica gel to remove the origin component. After purification with basic silica gel again, the product was dissolved in toluene, suspended and washed with methanol, and the precipitate was collected by suction filtration. A small amount of compound 9 was obtained as a red solid. Formation of the target compound was confirmed by mass spectrometry spectrum (m / z = 804).

Example 3: Synthesis of compound 10 (organometallic complex 10 of the present invention) As shown in the following (1) to (5), compound 10 (organometallic complex 10) was prepared according to the reaction scheme shown in [Chemical Formula 23] to [Chemical Formula 27]. Synthesized.

(1) Synthesis of Compound 11 To a mixture of 2-aminobenzophenone (15.0 g, 76.1 mmol), 3′-bromoacetophenone (18.2 g, 91.3 mmol) and acetic acid (75 ml), concentrated sulfuric acid (1.3 ml) And heated to reflux for 9 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The aqueous layer was neutralized and further extracted with ethyl acetate. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound 11 (24.2 g, yield 88%).

(2) Synthesis of Compound 12 Under a nitrogen stream, Compound 11 (24.2 g, 47.5 mmol) and Compound 3 (18.0 g, 87.3 mmol) were added to toluene (200 ml), ethanol (200 ml), water (100 ml). ), Sodium carbonate (21.4 g, 202 mmol) was added, and nitrogen bubbling was performed for 30 minutes with stirring. Tetrakis (triphenylphosphine) palladium (2.3 g, 2 mmol) was added thereto and heated to reflux for 7.5 hours. After the reaction, water was added and the mixture was extracted with toluene. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound 12 (24.1 g, yield 81%).

(3) Synthesis of Compound 13 Under a nitrogen stream, compound 12 (12 g, 27.2 mmol), iridium chloride n-hydrate (4.7 g, 13.6 mmol), 2-ethoxyethanol (71 ml), water (24 ml) ) And heated to reflux for 11 hours. Water was added to the reaction solution, extracted with dichloromethane, and the organic layer was concentrated under reduced pressure. The concentrated solution was added to methanol, and the crystallized crystals were collected by filtration to obtain Compound 13 (11.9 g, yield 79%) as a red solid.

(4) Synthesis of Compound 14 Under a nitrogen stream, 2-ethoxyethanol (140 ml) was added to Compound 13 (11.9 g, 5.4 mmol) and sodium acetylacetonate (3.3 g, 27 mmol) and heated for 8 hours. Refluxed. Water was added to the reaction mixture, and the mixture was extracted with dichloromethane. The organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain compound 14 (6.9 g, yield 55%) as a red solid.

(5) Synthesis of Compound 10 Glycerol (172 ml) was added to Compound 14 (6.9 g, 5.9 mmol) and Compound 12 (12.1 g, 27.4 mmol) under a nitrogen stream and stirred at 200 ° C. for 17 hours. . Methanol was added to the reaction solution to obtain a reddish brown oil component. The component was repeatedly purified by silica gel chromatography and washed with a dimethoxyethane / methanol solution and a tetrahydrofuran / acetonitrile solution to obtain Compound 10 as a red solid.

¹ H-NMR δ [ppm]; 8.25 (d, 3H), 8.12 (s, 3H), 8.00 (d, 3H), 7.78 (dd, 3H) 7.53 (m, 21H) ), 7.17 (m, 9H), 7.01 (dd, 3H), 6.77 (ddd, 3H), 6.70 (d, 3H), 2.58 (t, 6H), 1.30 (M, 24H), 0.88 (t, 9H)

Example 4: Synthesis of Compound 19 (Organic Metal Complex 19 of the Present Invention) As shown in the following (1) to (5), Compound 19 (organometallic complex 19) was prepared according to the reaction schemes shown in [Chemical 28] to [Chemical 32]. Synthesized.

(1) Synthesis of Compound 15 To a mixture of 2-aminobenzophenone (12.62 g, 64.00 mmol), 3′-bromo-4-methylacetophenone (15.0 g, 70.40 mmol) and acetic acid (70 ml), concentrated sulfuric acid (1 0.0 ml) and heated to reflux for 6 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The aqueous layer was neutralized and further extracted with ethyl acetate. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound 15 (13.4 g, yield 56%).

(2) Synthesis of Compound 16 Under a nitrogen stream, Compound 15 (13.3 g, 35.54 mmol) and Compound 3 (9.52 g, 46.20 mmol) were added to toluene (150 ml), ethanol (75 ml), water (50 ml). ), Sodium carbonate (10.6 g, 100 mmol) was added, and nitrogen bubbling was performed for 30 minutes with stirring. Tetrakis (triphenylphosphine) palladium (2.0 g, 1.78 mmol) was added thereto, and the mixture was heated to reflux for 6 hours. After the reaction, water was added and the mixture was extracted with toluene. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound 16 (15.7 g, yield 97%).

(3) Synthesis of Compound 17 Under a nitrogen stream, compound 16 (4.5 g, 9.88 mmol), iridium chloride n-hydrate (1.76 g, 4.94 mmol), 2-ethoxyethanol (32 ml), water (11 ml) was added and heated to reflux for 17 hours. Water was added to the reaction solution, extracted with dichloromethane, and the organic layer was concentrated under reduced pressure. The concentrated solution was added to methanol, and the crystallized crystals were collected by filtration to obtain Compound 17 (3.7 g, yield 65%) as a red solid.

(4) Synthesis of compound 18 Under a nitrogen stream, 2-ethoxyethanol (55 ml) was added to compound 17 (3.7 g, 1.62 mmol) and sodium acetylacetonate (0.99 g, 8.07 mmol). Heated to reflux for hours. Water was added to the reaction mixture, and the mixture was extracted with dichloromethane. The organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain compound 18 (3.3 g, yield 86%) as a red solid.

(5) Synthesis of Compound 19 Glycerol (40 ml) was added to Compound 18 (3.3 g, 2.77 mmol) and Compound 16 (6.1 g, 13.39 mmol) under a nitrogen stream and stirred at 260 ° C. for 7 hours. . Methanol was added to the reaction solution to obtain a reddish brown oil component, and the component was repeatedly purified by silica gel chromatography and washed with a dimethoxyethane / methanol solution and a tetrahydrofuran / acetonitrile solution to obtain Compound 19 as a red solid.

¹ H-NMR δ [ppm]; 8.21 (d, 3H), 8.01 (s, 3H), 7.77 (dd, 3H), 7.65 (s, 3H) 7.53 (m, 15H) ), 7.21 (m, 6H), 7.15 (m, 9H), 6.75 (ddd, 3H), 6.59 (s, 3H), 2.60 (t, 6H), 2.00 (S, 9H), 1.60 (m, 6H) 1.32 (m, 18H), 0.89 (t, 9H)

Example 5: Synthesis of Compound 24 (Organic Metal Complex 24 of the Present Invention) As shown in the following (1) to (5), Compound 24 (organometallic complex 24) was prepared according to the reaction scheme shown in [Chemical Formula 33] to [Chemical Formula 37]. Synthesized.

(1) Synthesis of Compound 20 Under a nitrogen stream, 3-chloro-4-methylphenylboronic acid (20.0 g, 117.37 mmol) and 1-chloroquinoline (14.77 g, 90.29 mmol) were added with toluene (160 ml). ), Ethanol (80 ml), water (60 ml) and sodium carbonate (12.7 g, 119.8 mmol) were added, and nitrogen bubbling was performed for 30 minutes with stirring. Tetrakis (triphenylphosphine) palladium (5.2 g, 4.5 mmol) was added thereto and heated to reflux for 7 hours. After the reaction, water was added and the mixture was extracted with toluene. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound 20 (16.1 g, yield 70%).

(2) Synthesis of Compound 21 Under a nitrogen stream, Compound 20 (16.1 g, 63.45 mmol) and Compound 3 (19.6 g, 95.18 mmol) were added to toluene (160 ml) and potassium phosphate (40.4 g, 190.35 mmol) was added, and nitrogen bubbling was performed for 30 minutes with stirring. Thereto were added palladium acetate (0.071 g, 0.317 mmol) and 2- (dicyclohexylphosphino) -2 ′, 6′-dimethoxybiphenyl (0.325 g, 0.793 mmol), and the mixture was heated to reflux for 8 hours. After the reaction, water was added and the mixture was extracted with toluene. The organic layer was concentrated under reduced pressure and purified by silica gel column chromatography to obtain compound 21 (22.0 g, yield 83%).

(3) Synthesis of Compound 22 Under nitrogen flow, Compound 21 (4.0 g, 10.54 mmol), iridium chloride n-hydrate (1.87 g, 5.27 mmol), 2-ethoxyethanol (30 ml), water (10 ml) was added and heated to reflux for 16 hours. Water was added to the reaction solution, extracted with dichloromethane, and the organic layer was concentrated under reduced pressure. The concentrated solution was added to methanol, and the crystallized crystals were collected by filtration to obtain Compound 22 (2.88 g, yield 56%) as a red solid.

(4) Synthesis of Compound 23 Under a nitrogen stream, 2-ethoxyethanol (45 ml) was added to Compound 22 (2.88 g, 1.465 mmol) and sodium acetylacetonate (0.89 g, 7.33 mmol). Heated to reflux for hours. Water was added to the reaction mixture, and the mixture was extracted with dichloromethane. The organic layer was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to obtain compound 23 (1.1 g, yield 36%) as a red solid.

(5) Synthesis of Compound 24 Under a nitrogen stream, glycerol (12 ml) was added to Compound 23 (1.1 g, 1.05 mmol) and Compound 21 (2.5 g, 6.59 mmol) and stirred at 220 ° C. for 6 hours. . Methanol was added to the reaction solution to obtain a reddish brown oil component, and the component was repeatedly purified by silica gel chromatography and washed with a dimethoxyethane / methanol solution and a tetrahydrofuran / acetonitrile solution to obtain Compound 24 as a red solid.

¹ H-NMR δ [ppm]; 8.05 (m, 9H), 7.65 (d, 3H), 7.60 (s, 3H), 7.16 (m, 15H) 6.70 (ddd, 3H) ), 6.5 (s, 3H), 2.60 (t, 6H), 1.95 (s, 9H), 1.65 (m, 6H) 1.31 (m, 18H), 0.89 ( t, 9H)

Example 6: Solubility of organometallic complex The solubility of each compound synthesized in Examples 1 to 5 in toluene was measured as follows.
To each compound weighed appropriately, toluene appropriately weighed was added, and it was confirmed with the naked eye that a solution uniformly dissolved at room temperature was obtained. However, a solution uniformly dissolved at room temperature was obtained. If not, add more toluene and repeat the check operation under lower concentration conditions. The concentration (% by mass) of each compound with respect to toluene at the time when a solution in a uniformly dissolved state at room temperature can be confirmed is defined as solubility. The results are shown in Table 1.
From Table 1, it can be seen that the solubility in toluene is dramatically improved by introducing a specific substituent into the phenylquinoline ring.

Example 7 Production and Evaluation of Organic Electroluminescent Device of the Present Invention The organic electroluminescent device shown in FIG. 1 was produced (however, a hole relaxation layer was used instead of the hole blocking layer).

  An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a thickness of 120 nm (manufactured by Sanyo Vacuum Co., Ltd., sputtered film) using ordinary photolithography technology and hydrochloric acid etching An anode was formed by patterning on a stripe having a width of 2 mm. The patterned ITO substrate is cleaned in the order of ultrasonic cleaning with an aqueous surfactant solution, water cleaning with ultrapure water, ultrasonic cleaning with ultrapure water, and water cleaning with ultrapure water, followed by drying with compressed air, and finally UV irradiation. Ozone cleaning was performed.

  First, a hole transporting polymer compound having a repeating structure represented by the structural formula P1 as a hole transporting compound (weight average molecular weight: 26500, number average molecular weight: 12000), and an electron accepting compound represented by the structural formula 4- A composition for forming a hole injection layer containing isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate was prepared. In this composition, the hole-transporting polymer compound P1 was 2.0% by mass, and the electron-accepting compound A1 was 0.8% by mass. This composition was formed by spin coating on the anode in the air at a spinner rotation speed of 1500 rpm and a spinner rotation time of 30 seconds. Then, the hole injection layer with a film thickness of 30 nm was obtained by heat-drying at 230 degreeC for 3 hours in air | atmosphere.

  Subsequently, a crosslinkable compound (polymer) H1 (weight average molecular weight: 95000) represented by the following structural formula as a hole transporting compound and toluene as a solvent were prepared. The solid content concentration of the crosslinkable compound in the composition was 0.4% by mass. This composition was formed on the hole injection layer formed as described above by spin coating at a spinner rotation speed of 1500 rpm and a spinner rotation time of 30 seconds in nitrogen, and crosslinked by heating at 230 ° C. for 1 hour in nitrogen. A crosslinked film (hole transport layer) having a thickness of 20 nm was formed.

  Next, in forming the light emitting layer, the charge transporting compound E-1, the charge transporting compound E-2, the compound 1 synthesized in Example 1 (organometallic complex 1 of the present invention) shown in the following structural formula, and A composition for forming a light emitting layer (organometallic complex-containing composition) containing cyclohexylbenzene as a solvent was prepared. In the composition, the charge transporting compound E-1 was 2.5% by mass, the charge transporting compound E-2 was 2.5% by mass, and the organometallic complex 1 was 0.25% by mass. This composition was formed on the hole transport layer formed as described above by spin coating at a spinner rotation speed of 1500 rpm, a spinner rotation time of 30 seconds and in nitrogen, and then at 130 ° C. under reduced pressure (0.1 MPa). It dried for 1 hour and obtained the light emitting layer with the film thickness of 60 nm.

Here, after the substrate on which the hole injection layer, the hole transport layer, and the light emitting layer are formed is transferred into a vacuum deposition apparatus, and the apparatus is roughly evacuated by an oil rotary pump, the degree of vacuum in the apparatus is 5.1. After evacuating using a cryopump until the pressure is lower than or equal to × 10 ⁻⁴ Pa, a compound represented by the following structural formula C-3 is formed on the light emitting layer by vacuum deposition and relaxed by 5 nm thick holes. A layer was obtained. The deposition rate was controlled in the range of 0.7 to 1.0 kg / second, and the degree of vacuum during the deposition was 1.9 to 2.0 × 10 ⁻⁴ Pa.

Subsequently, tris (8-hydroxyquinolinate) aluminum was heated and evaporated on the hole relaxation layer to form a 30 nm-thick electron transport layer. The degree of vacuum during vapor deposition was 1.3 × 10 ⁻⁴ Pa, and the vapor deposition rate was controlled in the range of 0.6 to 1.0 kg / second.

Here, the element on which the electron transport layer has been deposited is once taken out from the vacuum deposition apparatus into the atmosphere, and a 2 mm wide striped shadow mask is orthogonal to the ITO stripe of the anode 2 as a mask for cathode deposition. In close contact with the element, it was placed in another vacuum vapor deposition apparatus and evacuated until the degree of vacuum in the apparatus was 2.1 × 10 ⁻⁴ Pa or less in the same manner as the electron transport layer.

As the electron injection layer, lithium fluoride (LiF) was controlled using a molybdenum boat at a deposition rate of 0.07 to 0.17 liters / second and a degree of vacuum of 2.3 to 2.4 × 10 ⁻⁴ Pa. A film having a thickness of 5 nm was formed on the electron transport layer.
Next, aluminum as a cathode is similarly heated by a molybdenum boat and controlled at a deposition rate of 0.7 to 6.1 liters / second and a degree of vacuum of 2.3 to 2.7 × 10 ⁻⁴ Pa. An aluminum layer was formed. The substrate temperature during the above two-layer deposition was kept at room temperature.

Subsequently, a sealing process was performed to prevent the element from being deteriorated by moisture in the atmosphere during storage. As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained.
The maximum wavelength of the emission spectrum of the device was 595 nm, which was identified as that from the organometallic complex 1. The chromaticity was CIE (x, y) = (0.59, 0.40). The efficiency was 21.9 cd / A. The half life at 3000 cd / m ² was 5700 hours. The lifetime at this time was set to 1.

Example 8: Preparation and Evaluation of Organic Electroluminescent Device of Comparative Example In the device preparation of Example 7 above, the phosphorescent dopant was changed from Compound 1 (organometallic complex 1) to Compound 9 (organometallic complex 9). Thus, an organic electroluminescent element was produced.

The maximum wavelength of the emission spectrum of this device was 604 nm, which was identified as that from the organometallic complex 9. The chromaticity was CIE (x, y) = (0.64, 0.36). The efficiency was 13.3 cd / A. The half life at 3000 cd / m ² was 0.54 times shorter than that of the device using the organometallic complex 1 of Example 7.

  From the above results, it was found that the organometallic complex according to the present invention has higher efficiency and a longer half-life than the organometallic complex 9 used as a comparative example.

  The organic electroluminescence device using the organometallic complex according to the present invention is a highly efficient device with a long half-life and high practicality. Therefore, the present invention can be particularly suitably used in the fields of full-color displays, information display devices, lighting fixtures, and the like.

1. Substrate 2. Anode 3. Hole injection layer 4. 4. hole transport layer Light emitting layer 6. 6. Hole blocking layer Electron transport layer8. Electron injection layer 9. cathode

Claims (8)

Following formula (1):

[In the formula (1), R ¹ , R ⁴ , R ⁵ , R ^{7 to} R ¹⁰ are hydrogen atoms, R ² is a hydrogen atom or a methyl group, and R ³ has 5 to 15 carbon atoms in the p-position. And R ⁶ is a hydrogen atom or a phenyl group. ]
An organometallic complex represented by the formula: A luminescent material comprising the organometallic complex according to claim 1 . An organic electroluminescent element material comprising the organometallic complex according to claim 1 . An organometallic complex-containing composition comprising the organometallic complex according to claim 1 and a solvent. An organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, wherein the organic layer contains the organometallic complex according to claim 1. Light emitting element. The organic electroluminescent device according to claim 5 , wherein the organic layer is a light emitting layer. The organic light emitting display device characterized by comprising the organic electroluminescence device according to claim 5 or 6. The organic electroluminescent lighting device characterized by comprising the organic electroluminescence device according to claim 5 or 6.

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