JP3797310B2 - Material for organic electroluminescence device and organic electroluminescence device using the same - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a material for an organic electroluminescence (EL) element used for a flat light source and display, and an organic EL element using the same. More specifically, the present invention relates to a material for an organic EL element having a long life and capable of obtaining yellow-red high luminance light emission and an organic EL element using the same.
[0002]
[Prior art]
An EL element using an organic substance is considered to be promising for use as an inexpensive large-area full-color display element of a solid light emitting type, and many developments have been made. In general, an EL element is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side, holes are injected from the anode side, these electrons recombine with holes in the light emitting layer, and the energy level is in the conduction band. This is a phenomenon in which energy is released as light when returning from the valence band to the valence band.
[0003]
Conventional organic EL elements have a higher driving voltage and lower light emission luminance and light emission efficiency than inorganic EL elements. Further, the characteristic deterioration has been remarkably not put into practical use. In recent years, an organic EL device in which a thin film containing an organic compound having a high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less has been reported and attracted attention (Appl. Phys. Lett., Vol. 51, (See page 913, published in 1987). This method uses a metal chelate complex as a light emitting layer and an amine compound as a hole injection layer to obtain high luminance green light emission. The luminance is several thousand (cd / m) at a DC voltage of 6 to 10V.²), The maximum luminous efficiency is 1.5 (lm / W), and the performance is close to the practical range.
[0004]
Among organic EL elements, the light-emitting material for organic EL elements for obtaining yellow to red light emission is particularly described in C.I. H. Chen et al., Macromol. Symp. 125, 34-36 and 49-58, published in 1997, 4H-pyran derivatives such as DCM, DCJ, DCJT, and DCJTB emit light from yellow to red light for organic EL devices. Although reported as a material, there was a problem of low emission luminance.
[0005]
On the other hand, as for the light-emitting material for organic EL elements having a perylene structure, for example, mono- and diaminoperylene compounds described in JP-A Nos. 11-144869, 2001-11031, and 2001-176664 Etc. are known.
[0006]
[Problems to be solved by the invention]
None of the light-emitting materials for organic EL devices for obtaining yellow to red high-luminance emission described in the prior art has a drawback that it does not have sufficient emission luminance and has a short lifetime. On the other hand, since perylene has a highly planar molecular structure, undesirable phenomena such as concentration quenching tend to occur when it is used as a light emitting material for organic EL elements. Therefore, as described in the prior art, improvements such as increasing the number of amino groups bonded to perylene or introducing a sterically bulky substituent have been attempted, but with the accompanying increase in molecular weight, There is a concern that workability deteriorates, such as a decrease in solubility in a solvent and poor vapor deposition at the time of device preparation. Therefore, there has been a demand for a material for an organic EL element having a much higher light emission luminance and a longer lifetime.
[0007]
[Means for Solving the Problems]
  As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
  That is, this invention relates to the material for organic electroluminescent elements characterized by being a compound represented by the following general formula [1].
General formula [1]
[Chemical Formula 3]
[Wherein Ar¹Is a substituted or unsubstituted 3-perylenyl group, R¹And R²Is a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, and a substituted or unsubstituted A monovalent organic residue selected from the monovalent aromatic heterocyclic groups of: R¹And R²Is at least one monovalent organic residue represented by the following general formula [2].]
General formula [2]
[Formula 4]
[Wherein Ar²Is a substituted or unsubstituted divalent aromatic hydrocarbon group, or a substituted or unsubstituted divalent aromatic heterocyclic group, Ar^ThreeIs a substituted or unsubstituted monovalent aromatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic heterocyclic group, X¹Is a direct bond, O, S, ═C (R^Three) R^Four, = Si (R^Five) R⁶(Where R is^Three~ R⁶Is a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic hydrocarbon group). ]
[However, the substitution in the general formula [1] and the general formula [1] and the general formula [2] is a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic complex. Ring group, monovalent aromatic heterocyclic group, halogen atom, cyano group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group Is to be replaced with one of ]
  The present invention also provides Ar¹Is an unsubstituted 3-perylenyl group. The present invention relates to the material for an organic electroluminescence element.
  The present invention also provides R¹And R²These are all the monovalent organic residues represented by the general formula [2].
  In addition, the present invention relates to X¹Is a direct bond, and relates to the material for an organic electroluminescence element.
  Further, the present invention provides an organic electroluminescence device in which a single layer or a multilayer organic layer is formed between a pair of electrodes composed of an anode and a cathode, and at least one layer is a layer containing the organic electroluminescence device material. The present invention relates to an organic electroluminescence element.
  Further, the present invention provides an organic electroluminescent device in which at least one light emitting layer is formed between a pair of electrodes composed of an anode and a cathode, wherein the light emitting layer is a layer containing the material for an organic electroluminescent device. The present invention relates to an electroluminescence element.
  The present invention further relates to the above-mentioned organic electroluminescence device, wherein at least one electron injection layer is formed between the light emitting layer and the cathode.
[0008]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail. First, the monoamine compound represented by the general formula [1], which is a material for an organic EL device of the present invention, will be described.
[0009]
  First, Ar in the general formula [1]¹Represents a substituted or unsubstituted 3-perylenyl group. These perylenyl groups may be further substituted with other substituents. Examples of such a substituent include a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, a halogen atom, a cyano group, Alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl groupOne ofIs given.
[0010]
Here, the monovalent aliphatic hydrocarbon group refers to a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, such as an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group. Can be given.
[0011]
Therefore, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, C1-C18 alkyl groups, such as a decyl group, a dodecyl group, a pentadecyl group, and an octadecyl group, are mentioned.
[0012]
Examples of the alkenyl group include vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group, 1 -An alkenyl group having 2 to 18 carbon atoms such as an octadecenyl group.
[0013]
Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group and 1-octadecynyl group. Examples thereof include alkynyl groups having 2 to 18 carbon atoms.
[0014]
In addition, the cycloalkyl group has a carbon number such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, 2-bornyl group, 2-isobornyl group, 1-adamantyl group. Examples thereof include 3 to 18 cycloalkyl groups.
[0015]
Furthermore, examples of the monovalent aromatic hydrocarbon group include monovalent monocyclic, condensed ring, and ring-aggregated aromatic hydrocarbon groups having 6 to 30 carbon atoms. Here, as a monovalent monocyclic aromatic hydrocarbon group having 6 to 30 carbon atoms, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,4-xylyl group, p-cumenyl And monovalent monocyclic aromatic hydrocarbon groups having 6 to 30 carbon atoms such as a group and a mesityl group.
[0016]
Examples of the monovalent condensed ring aromatic hydrocarbon group include 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, 2-triphenylyl group, 1-pyrenyl group, 2-pyrenyl group, 1-perylenyl group, 2-perylenyl group, 3-perenylenyl group, 2-trephenylenyl group, Examples thereof include monovalent condensed ring hydrocarbon groups having 10 to 30 carbon atoms such as 2-indenyl group, 1-acenaphthylenyl group, 2-naphthacenyl group, and 2-pentacenyl group.
[0017]
The monovalent ring-aggregated aromatic hydrocarbon group has 12 carbon atoms such as o-biphenylyl group, m-biphenylyl group, p-biphenylyl group, terphenylyl group, 7- (2-naphthyl) -2-naphthyl group and the like. To 30 monovalent ring-assembled hydrocarbon groups.
[0018]
Examples of the monovalent aliphatic heterocyclic group include monovalent aliphatic heterocyclic groups having 3 to 18 carbon atoms such as 3-isochromanyl group, 7-chromanyl group, and 3-coumarinyl.
[0019]
Examples of the monovalent aromatic heterocyclic group include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-benzofuryl group, 2-benzothienyl group, 2-pyridyl group, 3 -Pyridyl group, 4-pyridyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3 -Isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-pyrimidinyl group, 2-pyrazinyl group, 2-quinazolinyl group, 2-quinoxalinyl group, 2 -C3-C30 monovalent | monohydric aromatic heterocyclic groups, such as oxazolyl group and 2-thiazolyl group, are mention | raise | lifted.
[0020]
In addition, examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.
[0021]
The alkoxyl group includes a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group, a 2-bornyloxy group, a 2-isobornyloxy group, and a 1-adamantyl group. C1-C18 alkoxyl groups, such as an oxy group, are mention | raise | lifted.
[0022]
Examples of the aryloxy group include aryloxy groups having 6 to 30 carbon atoms such as a phenoxy group, a 4-tert-butylphenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a 9-anthryloxy group. .
[0023]
Examples of the alkylthio group include C1-C18 alkylthio groups such as a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, and an octylthio group.
[0024]
Examples of the arylthio group include arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a 2-methylphenylthio group, and a 4-tert-butylphenylthio group.
[0025]
Examples of the acyl group include C2-C18 acyl groups such as an acetyl group, a propionyl group, a pivaloyl group, a cyclohexylcarbonyl group, a benzoyl group, a toluoyl group, an anisoyl group, and a cinnamoyl group.
[0026]
Moreover, as an alkoxycarbonyl group, C2-C18 alkoxycarbonyl groups, such as a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group, are mention | raise | lifted.
[0027]
Examples of the aryloxycarbonyl group include C2-C18 aryloxycarbonyl groups such as a phenoxycarbonyl group and a naphthyloxycarbonyl group.
[0028]
Moreover, as an alkylsulfonyl group, C2-C18 alkylsulfonyl groups, such as a mesyl group, an ethylsulfonyl group, a propylsulfonyl group, are mention | raise | lifted.
[0029]
Examples of the arylsulfonyl group include C2-C18 arylsulfonyl groups such as a benzenesulfonyl group and a p-toluenesulfonyl group.
[0030]
  The substituents described above may be further substituted with other substituents.Yes.
[0031]
A in general formula [1] described above^{r 1}as,An unsubstituted 3-perylenyl group is particularly preferred. The reason for this is that when the amino group is bonded to the 3-position of perylene, the angle between the perylene ring and the amino group is kept relatively on the same plane, so that the fluorescence becomes strong and the organic electroluminescence device This is because it is considered that the light emission luminance when used as is improved.
[0032]
Among the substituted 3-perylenyl groups, preferred substituents include alkyl groups, monovalent aromatic hydrocarbon groups, monovalent aromatic heterocyclic groups, aryloxy groups, and arylthio groups, and particularly preferred substitutions. Examples of the group include an alkyl group, a monovalent monocyclic aromatic hydrocarbon group, a monovalent condensed ring aromatic hydrocarbon group, a monovalent ring assembly aromatic hydrocarbon group, and a monovalent aromatic heterocyclic group. It is done.
[0033]
Moreover, 1-18 are preferable as a carbon number of a substituent among the preferable substituents described above, and 1-12 are more preferable. The reason for this is that if the carbon number of these substituents increases, the solubility in the solvent becomes poor, so that not only purification becomes difficult, but also the workability at the time of device creation deteriorates, and an attempt is made to create a device by vapor deposition. This is because there may be a concern that the vapor deposition property is deteriorated.
[0034]
Next, R in the general formula [1]¹And R²Will be described. R¹And R²Is a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, a substituted or unsubstituted 1 A monovalent organic residue selected from valent aromatic heterocyclic groups, R¹And R²Is at least one monovalent organic residue represented by the general formula [2]. The substituted or unsubstituted monovalent aliphatic hydrocarbon group, the substituted or unsubstituted monovalent aromatic hydrocarbon group, the substituted or unsubstituted monovalent aliphatic heterocyclic group, the substituted or unsubstituted The monovalent aromatic heterocyclic group is Ar¹A substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or It is synonymous with an unsubstituted monovalent aromatic heterocyclic group.
[0035]
Here, the general formula [2] will be described. First, Ar in the general formula [2]²Represents a substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent aromatic heterocyclic group. The substituent here is Ar.¹It is synonymous with the substituent demonstrated in (2), and two or more substituents may combine with each other to form a ring.
[0036]
Here, the divalent aromatic hydrocarbon group means a divalent monocyclic or condensed ring or ring-aggregated aromatic hydrocarbon group. For example, a phenylene group, a naphthylene group, an anthrylene group, a biphenylene group, a p-tell. Phenyl-4,4 ″ -diyl group, m-terphenyl-3,3 ″ -diyl group, m-terphenyl-4,4′-diyl group, [1,2′-binaphthalene] -4,5 Examples thereof include divalent aromatic hydrocarbon groups having 6 to 30 carbon atoms such as' -diyl.
[0037]
The divalent aromatic heterocyclic group means a divalent monocyclic ring, condensed ring, or ring assembly aromatic heterocyclic group. For example, 2,5-furylene group, 2,5-thienylene group, 2, 5-pyridylene group, 2,4-pyridylene group, 2,3-pyridylene group, 2,5-pyrazinylene group, 2,4-quinolylene group, 2,6-quinolylene group, 1,4-isoquinolylene group, 2,3 -A C4-C30 bivalent aromatic heterocyclic group, such as a quinoxalinylene group.
[0038]
Ar described above²Among the divalent aromatic hydrocarbon groups or aromatic heterocyclic groups in the formula, preferred are C6-C12 divalent aromatic hydrocarbon groups such as a phenylene group, a naphthylene group, and a biphenylene group. .
[0039]
Further, Ar in the general formula [2]^ThreeRepresents a substituted or unsubstituted monovalent aromatic hydrocarbon group or a substituted or unsubstituted monovalent aromatic heterocyclic group. The substituent here is Ar.¹It is synonymous with the substituent demonstrated in (2), and two or more substituents may combine with each other to form a ring. Further, the substituted or unsubstituted monovalent aromatic hydrocarbon group and the substituted or unsubstituted monovalent aromatic heterocyclic group referred to here are respectively Ar¹These are synonymous with the substituted or unsubstituted monovalent aromatic hydrocarbon group and the substituted or unsubstituted monovalent aromatic heterocyclic group described in the above.
[0040]
Furthermore, X in the general formula [2]¹Is a direct bond, O, S, ═C (R^Three) R^Four, = Si (R^Five) R⁶(Where R is^Three~ R⁶Is a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, or a substituted or unsubstituted monovalent aromatic hydrocarbon group). Where R^Three~ R⁶The substituted or unsubstituted monovalent aliphatic hydrocarbon group in FIG. 5 is a substituted or unsubstituted monovalent aromatic hydrocarbon group.¹Synonymous with the substituted or unsubstituted monovalent aliphatic hydrocarbon group and the substituted or unsubstituted monovalent aromatic hydrocarbon group described in the above, and two or more substituents are bonded to each other to form a ring. It does not matter.
[0041]
R in general formula [1]¹And R²For example, at least one monovalent organic residue represented by the general formula [2] may be used, but any monovalent organic residue represented by the general formula [2] is preferable. This is because R¹And R²However, in the case of a monovalent organic residue represented by the general formula [2], the molecule becomes three-dimensional while the angle between the perylene ring and the amino group is kept relatively on the same plane. This is because an undesirable phenomenon such as quenching is suppressed, and it is considered that the light emission luminance when used as an organic electroluminescence element is improved. Furthermore, X in the general formula [2]¹When is a direct bond, the conjugated system in the molecule becomes large, and it is considered that the emission luminance is improved, which is particularly preferable.
[0042]
The monoamine compound represented by the general formula [1] of the present invention has been described above. The molecular weight of the monoamine compound of the present invention is preferably 2000 or less, more preferably 1500 or less, and particularly preferably 1000 or less. The reason for this is that, if the molecular weight is large, the solubility in the solvent becomes poor, so not only purification becomes difficult, but the workability at the time of device creation is deteriorated, and the vapor deposition property when the device is created by vapor deposition This is because there is a concern that it will worsen.
[0043]
The element created by using the organic EL element material of the present invention alone in the light emitting layer usually exhibits yellow to orange high-intensity light emission, but when used with an appropriate doping material as described later, It is possible to extend the emission color to red while maintaining high luminance.
[0044]
Hereinafter, representative examples of compounds that can be used as the material for the organic EL device of the present invention are shown in Table 1, but the present invention is not limited to these (however, in Table 1, t-Bu is A tertiary butyl group, and Ph represents a phenyl group).
[0045]
[Table 1]
[0046]
[0047]
[0048]
[0049]
[0050]
[0051]
[0052]
[0053]
[0054]
[0055]
[0056]
[0057]
[0058]
[0059]
[0060]
[0061]
[0062]
[0063]
[0064]
[0065]
[0066]
[0067]
[0072]
By the way, an organic EL element is an element in which a single layer or a multilayer organic layer is formed between an anode and a cathode. Here, a single layer type organic EL element has a light emitting layer made of a light emitting material between an anode and a cathode. Have. On the other hand, the multilayer organic EL device has (anode / hole injection layer / light emitting layer / cathode), (anode / light emitting layer / electron injection layer / cathode), (anode / hole injection layer / light emitting layer / electron injection layer). / Cathode) is an organic EL element laminated in a multilayer structure. The organic EL device material of the present invention can be used in any of the above-mentioned layers, but can be suitably used as a light-emitting material for these single-layer or multilayer organic EL devices. In particular, when a single-layer organic EL device is prepared using the light emitting material for the organic EL device, a hole injection material or an electron for efficiently transporting holes injected from the anode or electrons injected from the cathode to the light emitting material. An injection material can be included.
[0073]
Here, the hole injection material indicates an excellent hole injection effect for the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the electron injection layer or the electron injection material, and It means a compound excellent in thin film forming property. Examples of such hole injection materials include phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazoles, triazoles, imidazoles, imidazolones, imidazolethiones, pyrazolines, pyrazolones, tetrahydroimidazoles, oxazoles, oxadiazoles Hydrazone, acyl hydrazone, polyarylalkane, stilbene, butadiene, benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine, and their derivatives, and polyvinylcarbazole, polysilane, conductive polymer, etc. The present invention is not limited to these examples.
[0074]
Among the above hole injection materials, particularly effective hole injection materials include aromatic tertiary amine derivatives or phthalocyanine derivatives. Examples of aromatic tertiary amine derivatives include triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4′- Diamine, N, N, N ', N'-(4-methylphenyl) -1,1'-phenyl-4,4'-diamine, N, N, N ', N'-(4-methylphenyl)- 1,1′-biphenyl-4,4′-diamine, N, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N ′-(methylphenyl) ) -N, N ′-(4-n-butylphenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, or these Aromatic tertiary amine skeleton Oligomers or polymers having, and the like. Moreover, as a phthalocyanine (Pc) derivative, H₂Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl₂Examples thereof include phthalocyanine derivatives and naphthalocyanine derivatives such as SiPc, (HO) AlPc, (HO) GaPc, VOPc, TiOPc, MoOPc, and GaPc-O-GaPc. The hole injection material described above can be further sensitized by adding an electron accepting material.
[0075]
On the other hand, the electron injection material shows an excellent electron injection effect for the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the hole injection layer or the hole injection material, and is a thin film. It means a compound excellent in formability. Examples of such electron injection materials include quinoline metal complexes, oxadiazoles, benzothiazole metal complexes, benzoxazole metal complexes, benzimidazole metal complexes, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxadioxide. Examples thereof include azole, thiadiazole, tetrazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone and the like. An inorganic / organic composite material doped with a metal such as cesium in bathophenanthroline (for example, Proceedings of the Society of Polymer Science, Vol. 50, No. 4, page 660, issued in 2001) is an example of an electron injection material. However, the present invention is not limited to these.
[0076]
Among the electron injection materials, particularly effective electron injection materials include metal complex compounds and nitrogen-containing five-membered ring derivatives. Here, among the metal complex compounds, the compound represented by the following general formula [3] can be preferably used.
General formula [3]
[Chemical formula 5]
[Where Q¹And Q²Each independently represents a substituted or unsubstituted hydroxyquinoline derivative or a substituted or unsubstituted hydroxybenzoquinoline derivative, and L represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, A substituted or unsubstituted aryl group, or a substituted or unsubstituted aromatic heterocyclic group, -OR (where R is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted group, A substituted or unsubstituted aromatic heterocyclic group), -O-Ga-Q.^Three(Q^Four(Q^ThreeAnd Q^FourQ¹ And Q²Means the same. Represents a ligand represented by ]
[0077]
Here, the general formula [3] will be described. Q of the compound represented by the general formula [3]¹~ Q^FourIs a substituted or unsubstituted hydroxyquinoline derivative or a substituted or unsubstituted hydroxybenzoquinoline derivative. The substituent here is R in the general formula [1].¹And R²It is synonymous with the substituent in.
[0078]
L represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aromatic heterocyclic group. The substituent here is R in the general formula [1].¹And R²It is synonymous with the substituent in. Examples of the substituted or unsubstituted cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, and a cyclodecanyl group.
[0079]
Therefore, specific examples of the compound represented by the general formula [3] include bis (2-methyl-8-hydroxyquinolinate) (1-naphtholate) gallium complex, bis (2-methyl-8-hydroxyquinolinate). ) (2-Naphtholate) gallium complex, bis (2-methyl-8-hydroxyquinolinate) (phenolate) gallium complex, bis (2-methyl-8-hydroxyquinolinate) (4-cyano-1-naphtholate) Gallium complex, bis (2,4-dimethyl-8-hydroxyquinolinato) (1-naphtholato) gallium complex, bis (2,5-dimethyl-8-hydroxyquinolinato) (2-naphtholato) gallium complex, bis (2-Methyl-5-phenyl-8-hydroxyquinolinate) (phenolate) gallium complex, bis (2-methyl- -Cyano-8-hydroxyquinolinate) (4-cyano-1-naphtholate) gallium complex, bis (2-methyl-8-hydroxyquinolinato) chlorogallium complex, bis (2-methyl-8-hydroxyquinolinate) (Nato) (o-cresolate) gallium complex and the like, but the present invention is not limited thereto. The compound represented by the general formula [3] can be synthesized by the method described in JP-A-10-88,121.
[0080]
In addition, among the electron injection materials that can be used in the present invention, preferred metal complex compounds include 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, Bis (8-hydroxyquinolinate) manganese, Tris (8-hydroxyquinolinato) aluminum, Tris (2-methyl-8-hydroxyquinolinato) aluminum, Tris (8-hydroxyquinolinato) gallium, Bis ( 10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc and the like.
[0081]
Among the electron injecting materials that can be used in the present invention, preferable nitrogen-containing five-membered derivatives include oxazole, thiazole, oxadiazole, thiadiazole, and triazole derivatives. Specifically, 2,5-bis ( 1-phenyl) -1,3,4-oxazole, dimethyl POPOP, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis (1-phenyl) -1,3, 4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5-bis (1-naphthyl) -1,3 , 4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxadiazolyl) -4-tert-butylbenzene] 2 -(4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1,3,4-thiadiazole, 1,4 -Bis [2- (5-phenylthiadiazolyl)] benzene, 2- (4'-tert-butylphenyl) -5- (4 "-biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene, etc. The electron injecting material described above further includes an electron donating material. Can be sensitized.
[0082]
Moreover, the organic EL device material of the present invention can be used by doping into the light emitting layer. In this case, the organic EL device material is preferably contained in the range of 0.001 to 50% by weight, and more preferably in the range of 0.01 to 10% by weight with respect to the host material described below. More preferably.
[0083]
Host materials that can be used together with the organic EL device material of the present invention as a doping material include quinoline metal complexes, benzoquinoline metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, benzimidazole metal complexes, and benzotriazole metals. Electron transport materials such as complexes, imidazole derivatives, oxadiazole derivatives, thiadiazole derivatives, and triazole derivatives. Or hole transporting materials such as stilbene derivatives, butadiene derivatives, benzidine type triphenylamine derivatives, styrylamine type triphenylamine derivatives, diaminoanthracene type triphenylamine derivatives, diaminophenanthrene type triphenylamine derivatives, and polyvinylcarbazole, Examples thereof include polymer materials of conductive polymers such as polysilane.
[0084]
Moreover, in the light emitting layer in this organic EL element, in addition to the material for organic EL elements of the present invention, two or more kinds of other light emitting materials and doping materials can be used in combination. In this case, the organic EL element material of the present invention may function as a host material. Other light-emitting materials and doping materials that can be used with the organic EL device material of the present invention include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenyl Butadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, Polymethine, merocyanine, imidazole chelating oxinoid compounds, quinacridone, rubrene, etc. and their derivatives It is below.
[0085]
In the light emitting layer of the present organic EL device, in addition to the organic EL device material of the present invention, not only other light emitting materials and doping materials, but also the above-described hole injection materials and electron injection materials are used. Two or more kinds of materials can be used in combination. Further, the hole injection layer, the light emitting layer, and the electron injection layer may each be formed with a layer configuration of two or more layers.
[0086]
Furthermore, the conductive material used for the anode of the organic EL element of the present invention is suitably one having a work function larger than 4 eV, such as carbon, aluminum, vanadium, iron, cobalt, nickel. , Tungsten, silver, gold, platinum, palladium and the like and alloys thereof, ITO substrates, metal oxides such as tin oxide and indium oxide called NESA substrates, and organic conductive polymers such as polythiophene and polypyrrole.
[0087]
Further, the conductive material used for the cathode of the organic EL device of the present invention is suitably one having a work function smaller than 4 eV, such as magnesium, calcium, tin, lead, titanium, yttrium. Lithium, lithium fluoride, ruthenium, manganese and the like and alloys thereof. Here, examples of the alloy include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. Since the ratio of the alloy can be controlled by the heating temperature, atmosphere, and degree of vacuum at the time of preparation, an alloy having an appropriate ratio can be prepared. These anodes and cathodes may be formed with a layer structure of two or more layers if necessary.
[0088]
In order for the organic EL device of the present invention to emit light efficiently, the material constituting the device is preferably sufficiently transparent in the light emission wavelength region of the device, and at the same time, the substrate is preferably transparent. The transparent electrode can be prepared by a method such as vapor deposition or sputtering using the above conductive material. In particular, it is desirable that the light transmission surface electrode has a light transmittance of 10% or more. The substrate is not particularly limited as long as it has mechanical and thermal strength and is transparent. For example, a transparent polymer such as a glass substrate, polyethylene, polyethersulfone, and polypropylene is recommended.
[0089]
In addition, as a method for forming each layer of the organic EL element of the present invention, any one of a dry film forming method such as vacuum deposition, sputtering, plasma, and ion plating, or a wet film forming method such as spin coating, dipping, and flow coating is used. The method can be applied. The thickness of each layer is not particularly limited, but must be set to an appropriate thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. On the other hand, if the film thickness is too thin, pinholes and the like are generated, and it becomes difficult to obtain sufficient light emission luminance even when an electric field is applied. Accordingly, the normal film thickness is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.
[0090]
In the case of a wet film forming method, each layer forms a thin film by dissolving or dispersing the material constituting it in an appropriate solvent such as toluene, chloroform, tetrahydrofuran, dioxane or the like. The solvent used here may be either a single solvent or a mixed solvent. In any wet film forming method, an appropriate polymer or additive may be used for improving the film forming property and preventing pinholes in the film. Examples of such polymers include insulating polymers such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and photoconductive materials such as poly-N-vinylcarbazole and polysilane. And conductive polymers such as conductive polymer, polythiophene, and polypyrrole. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer. When the material of the present invention is wet-formed, the affinity between the molecules of each compound is good, so even if the compound alone is highly cohesive and the film tends to be non-uniform, it is mixed with a derivative with low cohesiveness. A good film can be obtained by using the material.
[0091]
In addition, in order to improve the stability of the organic EL device obtained by the present invention against temperature, humidity, atmosphere, etc., a protective layer may be further provided on the surface of the device, or the entire device may be covered with silicon oil, polymer, etc. good.
[0092]
As described above, an organic EL element produced using the material for an organic EL element can improve characteristics such as light emission efficiency and maximum light emission luminance. In addition, since the organic EL element can emit light that can be practically used at a low driving voltage, it is possible to reduce deterioration that has been a major problem until now. Therefore, this organic EL device can be applied to flat panel displays such as wall-mounted televisions and flat light emitters, as well as light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights. Can be considered.
[0093]
【Example】
EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to the following Example at all. First, prior to examples, a synthesis example of the organic EL element material of the present invention will be described.
[0094]
Synthesis example 1
Method for synthesizing compound (3)
In 300 ml of toluene, 30.8 g of 4-bromobiphenyl, 16.0 g of 3-aminoperylene, 13.8 g of sodium-t-butoxide, 0.67 g of palladium acetate and 2.43 g of tri-t-butylphosphine were added, and a nitrogen atmosphere The mixture was refluxed for 2 hours with stirring. The mixture was allowed to cool and then filtered. The filtrate was concentrated and purified by column chromatography using silica gel to obtain 26.1 g of compound (3). The structure was confirmed by mass spectrum, NMR spectrum and elemental analysis. Fig. 1 shows CDCl._ThreeOf compound (3) measured in solution¹1 shows an H-NMR spectrum (based on the absorption peak of tetramethylsilane).
[0095]
Synthesis example 2
Method for synthesizing compound (7)
In 300 ml of toluene, 32.7 g of 4-methyl-2'-bromobiphenyl, 16.0 g of 3-aminoperylene, 13.8 g of sodium-t-butoxide, 0.67 g of palladium acetate and 2.43 g of tri-t-butylphosphine And heated to reflux for 2 hours with stirring under a nitrogen atmosphere. The mixture was allowed to cool and then filtered, and the filtrate was concentrated and purified by column chromatography using silica gel to obtain 22.1 g of Compound (7). The structure was confirmed by mass spectrum, NMR spectrum and elemental analysis.
[0096]
Synthesis example 3
Method for synthesizing compound (9)
In 300 ml of toluene, 32.7 g of 2-methyl-4'-bromobiphenyl, 16.0 g of 3-aminoperylene, 13.8 g of sodium-t-butoxide, 0.67 g of palladium acetate and 2.43 g of tri-t-butylphosphine And heated to reflux for 2 hours with stirring under a nitrogen atmosphere. The mixture was allowed to cool and then filtered, and the filtrate was concentrated and purified by column chromatography using silica gel to obtain 27.1 g of Compound (9). The structure was confirmed by mass spectrum, NMR spectrum and elemental analysis.
[0097]
Examples using the compounds of the present invention are shown below. In this example, all mixing ratios indicate weight ratios unless otherwise specified. Moreover, the characteristic of the organic EL element with an electrode area of 2 mm × 2 mm was measured. In the implementation, the following known materials were used.
(Comparative Compound A)
[0098]
[Chemical 6]
[0099]
(Comparative Compound B)
[0100]
[Chemical 7]
[0101]
(Comparative Compound C)
[0102]
[Chemical 8]
[0103]
(Comparative Compound D)
[0104]
[Chemical 9]
[0105]
(DCJTB)
[0106]
[Chemical Formula 10]
[0107]
Example 1
On the washed glass plate with an ITO electrode, the compound (1) in Table 1 as a luminescent material, 2,5-bis (1-naphthyl) -1,3,4-oxadiazole, polycarbonate resin (Teijin Chemicals: Panlite) K-1300) was dissolved in tetrahydrofuran at a weight ratio of 1: 2: 10, and a light emitting layer having a thickness of 100 nm was obtained by a spin coating method. On top of this, an electrode having a thickness of 150 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 (weight ratio) to obtain an organic EL device. The light emission characteristics of this element are as follows: emission luminance at a DC voltage of 10 V (cd / m²), Maximum luminance 750 (cd / m)²), A light emission efficiency of 0.48 (lm / W) was obtained.
[0108]
Example 2
N, N '-(3-Methylphenyl) -N, N'-diphenyl-1,1'-biphenyl-4,4'-diamine (TPD) and polyvinylcarbazole (PVK) on a cleaned glass plate with an ITO electrode ) Was dissolved in 1,2-dichloroethane at a weight ratio of 1: 1, and a hole injection layer having a thickness of 50 nm was obtained by spin coating. Next, the compound (8) in Table 1 is deposited to prepare a 60 nm-thickness electron-injection-type light-emitting layer, on which an electrode having a thickness of 100 nm is formed of an alloy in which magnesium and silver are mixed at a weight ratio of 10: 1. To obtain an organic EL device. The light emission characteristics of this element are as follows: light emission luminance at a DC voltage of 10 V (cd / m²), Maximum luminance 1800 (cd / m)²), A light emission efficiency of 0.69 (lm / W) was obtained.
[0109]
Example 3
On the washed glass plate with an ITO electrode, TPD and polyvinylcarbazole (PVK) were dissolved in 1,2-dichloroethane at a weight ratio of 1: 1, and a hole injection layer having a thickness of 50 nm was obtained by a spin coating method. Subsequently, the mixture which consists of a 1:50 weight ratio of the compound (10) of Table 1 and a tris (8-hydroxyquinolinate) aluminum complex (Alq3) was vapor-deposited, and the electron injection type light emitting layer with a film thickness of 60 nm was created. Then, an electrode having a thickness of 100 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 (weight ratio) to obtain an organic EL device. The light emission characteristics of this element are as follows: light emission luminance at a DC voltage of 10 V (cd / m 2)²), Maximum luminance of 3200 (cd / m)²), Emission with a luminous efficiency of 1.3 (lm / W) was obtained.
[0110]
Example 4
On the washed glass plate with an ITO electrode, the compound (20) in Table 1 was dissolved in methylene chloride, and a hole injection type light emitting layer having a film thickness of 50 nm was obtained by a spin coating method. Next, a bis (2-methyl-8-hydroxyquinolinate) (1-naphtholate) gallium complex is vacuum-deposited to form an electron injection layer having a thickness of 40 nm, and then magnesium and silver are added 10: 1 ( An electrode having a film thickness of 100 nm was formed from an alloy mixed at a weight ratio to obtain an organic EL device. The electron injection layer is 10^-6Deposition was performed in a vacuum of Torr at a substrate temperature of room temperature. This element has an emission luminance of 3200 (cd / m at a DC voltage of 6 V).²), Maximum emission brightness 12600 (cd / m)²), A light emission efficiency of 2.3 (lm / W) was obtained.
[0111]
Example 5
On the washed glass plate with an ITO electrode, the compound (29) shown in Table 1 was vacuum-deposited to obtain a 50 nm-thick hole injection type light emitting layer. Next, a bis (2-methyl-8-hydroxyquinolinate) (p-cyanophenolate) gallium complex is vacuum-deposited to form an electron injection layer having a thickness of 30 nm. An electrode having a thickness of 100 nm was formed from an alloy mixed at 1 (weight ratio) to obtain an organic EL element. Each layer is 10^-6Deposition was performed in a vacuum of Torr at a substrate temperature of room temperature. This element has an emission luminance of 4300 (cd / m) at a DC voltage of 6V.²), Maximum emission luminance 13400 (cd / m)²), Emission with a luminous efficiency of 2.5 (lm / W) was obtained.
[0112]
Example 6
TPD was vacuum-deposited on the cleaned glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 20 nm. Subsequently, the compound (47) of Table 1 was vapor-deposited, the light emitting layer with a film thickness of 40 nm was created, then Alq3 was vapor-deposited, and the electron injection layer with a film thickness of 30 nm was obtained. On top of this, an electrode having a film thickness of 200 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 (weight ratio) to obtain an organic EL device. Each layer is 10^-6Deposition was performed in a vacuum of Torr at a substrate temperature of room temperature. This element has a direct-current voltage of 6 V and an emission luminance of 7100 (cd / m²) Was obtained. In addition, emission luminance of 500 (cd / m²) Had a half life of 1000 hours when driven at a constant current.
[0113]
Comparative Example 1
An organic EL device was produced in the same manner as in Example 6 except that the comparative compound A was used in place of the compound (47). This device has a luminance of 1600 (cd / m) at a DC voltage of 6V.²)Met. In addition, emission luminance of 500 (cd / m²) Was 260 hours when driven at a constant current.
[0114]
Example 7
TPD was vacuum-deposited on the cleaned glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 40 nm. Next, the compound (53) in Table 1 and Alq3 were co-evaporated at a composition ratio of 1:50 (weight ratio) to obtain a light emitting layer having a thickness of 30 nm. Further, Alq3 was deposited to obtain an electron injection layer having a thickness of 30 nm. On top of this, an electrode having a film thickness of 200 nm was formed from an alloy in which magnesium and silver were mixed at a ratio of 10: 1 (weight ratio) to obtain an organic EL device. Each layer is 10^-6Deposition was performed in a vacuum of Torr at a substrate temperature of room temperature. This device has an emission luminance of 7000 (cd / m) at a DC voltage of 6V.²), Emission luminance at 20 V is 46000 (cd / m)²) Was obtained. In addition, emission luminance of 500 (cd / m²) Had a half life of 1000 hours when driven at a constant current.
[0115]
Comparative Example 2
An organic EL device was produced in the same manner as in Example 15 except that the comparative compound C was used in place of the compound (53). This device has a luminance of 21000 (cd / m) at a DC voltage of 20V.²)Met. In addition, emission luminance of 500 (cd / m²), The half-life when driven at a constant current was 240 hours.
[0116]
  Examples 8-34And Comparative Examples 3-6
  4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) is vacuum-deposited on the cleaned glass plate with an ITO electrode to form a 30 nm-thick hole injection layer. Formed. Subsequently, the compound of Table 1 was vacuum-deposited and the light emitting layer with a film thickness of 30 nm was obtained. Further, a bis (2-methyl-8-hydroxyquinolinate) (phenolate) gallium complex was vacuum-deposited to prepare an electron injection layer having a film thickness of 30 nm, and magnesium and silver were further added at a ratio of 10: 1 (weight ratio). An electrode having a film thickness of 100 nm was formed from the alloy mixed in step 1) to obtain an organic EL device. Each layer is 10^-6Deposition was performed in a vacuum of Torr at a substrate temperature of room temperature. The light emission characteristics of this element are shown in Table 2. All of the organic EL elements of this example have a maximum light emission luminance of 35000 (cd / m²) The above high luminance characteristics were exhibited. Similarly, as a comparative example, an organic EL device was produced in the same manner as in Example 8 except that the comparative compounds A to D were formed and used. The light emission characteristics of this element are also shown in Table 2. In any case, it is clear that both the maximum light emission luminance and the maximum light emission efficiency are inferior to those of the device prepared in this example.
[0117]
[Table 2]
[0118]
Example 37
Α-NPD was vacuum-deposited on the cleaned glass plate with an ITO electrode to obtain a 20 nm-thick hole injection layer. Next, the compound (9) in Table 1 and Alq3 were co-deposited at a weight ratio of 1:50 to prepare a light emitting layer having a thickness of 40 nm, and then Alq3 was evaporated to obtain an electron injection layer having a thickness of 30 nm. First, an electrode was formed by vacuum deposition of lithium fluoride (LiF) at 0.5 nm and aluminum (Al) at 200 nm to obtain an organic EL device. Each layer is 10^-6Deposition was performed in a vacuum of Torr at a substrate temperature of room temperature. This device has an emission luminance of 6700 (cd / m) at a DC voltage of 7V.²), Maximum emission luminance 42100 (cd / m)²), A light emission efficiency of 3.9 (lm / W) was obtained.
[0119]
Example 38
An organic EL device was produced in the same manner as in Example 8, except that a thin film having a thickness of 30 nm was formed by depositing the compound (1) and the compound (3) in Table 1 at a weight ratio of 1: 1 as the light emitting layer. . This device has an emission luminance of 6300 (cd / m at a DC voltage of 7 V).²), Maximum emission luminance 36500 (cd / m)²), A light emission efficiency of 3.8 (lm / W) was obtained.
[0120]
Example 39
As the light emitting layer, except that a thin film having a film thickness of 30 nm obtained by depositing the compound (11) of Table 1 and bis (2-methyl-8-hydroxyquinolinate) (phenolate) gallium complex at a weight ratio of 1:50 is provided An organic EL device was produced in the same manner as in Example 8. This element has an emission luminance of 6500 (cd / m at a DC voltage of 7 V).²), Maximum emission luminance 38300 (cd / m)²), A light emission efficiency of 3.9 (lm / W) was obtained.
[0121]
Example 40
An organic EL device was produced in the same manner as in Example 8, except that a thin film having a thickness of 30 nm obtained by depositing the compound (16) in Table 1 and α-NPD at a weight ratio of 1:10 was provided as the light emitting layer. This element has an emission luminance of 7100 (cd / m at a DC voltage of 7 V).²) Maximum emission brightness 41200 (cd / m)²), A light emission efficiency of 4.0 (lm / W) was obtained.
[0122]
Example 41
Example 8 is provided except that a thin film having a film thickness of 30 nm obtained by depositing the compound (28) of Table 1 and 2,3,6,7,10,11-hexamethoxytriphenylene at a weight ratio of 1:10 is provided as the light emitting layer. An organic EL device was produced in the same manner as described above. This element has an emission luminance of 7200 (cd / m at a DC voltage of 7 V).²) Maximum emission brightness 42100 (cd / m)²), A light emission efficiency of 4.1 (lm / W) was obtained.
[0123]
Example 42
An organic EL device was produced in the same manner as in Example 8 except that a thin film having a thickness of 30 nm was deposited as the light emitting layer by depositing the compound (3) in Table 1 and DCJTB at a weight ratio of 100: 5. This element has an emission luminance of 5400 (cd / m at a DC voltage of 7 V).²) Maximum emission brightness 37800 (cd / m)²), A light emission efficiency of 3.2 (lm / W) was obtained.
[0124]
Example 43
Α-NPD was vacuum-deposited on the washed glass plate with the ITO electrode to obtain a hole injection layer having a thickness of 40 nm. Next, after the compound (3) in Table 1 was vacuum-deposited to form a first light-emitting layer having a thickness of 10 nm, the compound (33) in Table 1 was vacuum-deposited to form a second light-emitting layer having a thickness of 30 nm. Further, a bis (2-methyl-8-hydroxyquinolinate) (phenolate) gallium complex was vacuum-deposited to prepare an electron injection layer having a film thickness of 30 nm, and then magnesium and silver were added at a ratio of 10: 1 (weight ratio). An electrode having a film thickness of 100 nm was formed from the alloy mixed in step 1) to obtain an organic EL device. Each layer is 10^-6Deposition was performed in a vacuum of Torr at a substrate temperature of room temperature. This element has an emission luminance of 6500 (cd / m at a DC voltage of 7 V).²), Maximum emission luminance 38900 (cd / m)²), A light emission efficiency of 3.8 (lm / W) was obtained.
[0125]
Example 44
4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine is vacuum-deposited on the cleaned glass plate with the ITO electrode to form a first positive electrode having a thickness of 60 nm. Next, α-NPD was vacuum-deposited to obtain a second hole injection layer having a thickness of 20 nm, and the compound (14) in Table 1 was vacuum-deposited to obtain a thickness of 10 nm. A light emitting layer was prepared, and Alq3 was vacuum deposited to form an electron injection layer having a thickness of 30 nm, on which LiF was 0.2 nm and then Al was vacuum deposited to form an electrode, An organic EL element was obtained.^-6Deposition was performed in a vacuum of Torr at a substrate temperature of room temperature. This element has an emission luminance of 8600 (cd / m at a DC voltage of 7 V).²), Maximum emission luminance 43500 (cd / m)²), A light emission efficiency of 4.3 (lm / W) was obtained.
[0126]
Example 45
An organic EL device was produced in the same manner as in Example 44, except that a 30 nm-thick thin film in which the compound (24) in Table 1 and Alq3 were deposited at a weight ratio of 1: 100 was provided as the light-emitting layer. This element has an emission luminance of 32800 (cd / m) at a DC voltage of 7V.²), Emission with a luminous efficiency of 3.6 (cd / A) was obtained. In addition, emission luminance of 500 (cd / m²) Had a half life of 1200 hours when driven at a constant current.
[0127]
Comparative Example 7
An organic EL device was produced in the same manner as in Example 45 except that the comparative compound B was used instead of the compound (24). This device has an emission luminance of 13000 (cd / m at a DC voltage of 7 V).²) And emission luminance of 500 (cd / m)²), The half-life when driven at a constant current was 250 hours.
[0128]
Example 46
Example 45 except that a hole injection layer having a thickness of 20 nm of copper phthalocyanine is provided instead of 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine An organic EL device was manufactured in the same manner, and this device had an emission luminance of 30100 (cd / m at a DC voltage of 7 V).²), Light emission with a light emission efficiency of 3.9 (cd / A) was obtained. In addition, emission luminance of 500 (cd / m²), The half-life when driven at a constant current was 1500 hours.
[0129]
Comparative Example 8
An organic EL device was produced in the same manner as in Example 46 except that the comparative compound D was used instead of the compound (24). This element has an emission luminance of 15300 (cd / m at a DC voltage of 7 V).²) And emission luminance of 500 (cd / m)²), The half-life when driven at a constant current was 270 hours.
[0130]
As is clear from the above-described embodiments, the organic EL device of the present invention achieves improvement in luminous efficiency, luminous luminance, and long life, and the luminescent material, doping material, and hole injection used together. The material, the electron injection material, the sensitizer, the resin, the electrode material, and the like and the device manufacturing method are not limited.
[0131]
【The invention's effect】
Since the organic EL element produced using the material for the organic EL element of the present invention has higher luminance and longer life than conventional ones, it can be suitably used as a flat panel display such as a wall-mounted television or a flat light emitter. It can be applied to light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights.
[Brief description of the drawings]
1 is a CDCl of compound (3) obtained in Synthesis Example 1. FIG._ThreeIn solution¹1 shows an H-NMR spectrum (based on the absorption peak of tetramethylsilane).

Claims (7)

A material for an organic electroluminescence device, which is a monoamine compound represented by the following general formula [1].
General formula [1]
[Wherein Ar ¹ represents a substituted or unsubstituted 3-perylenyl group, R ¹ and R ² represent a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic carbon group, A monovalent organic residue selected from a hydrogen group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, and a substituted or unsubstituted monovalent aromatic heterocyclic group, wherein R ¹ and R ² At least one of these is a monovalent organic residue represented by the following general formula [2] . ]
General formula [2]
[Wherein Ar ² represents a substituted or unsubstituted divalent aromatic hydrocarbon group or a substituted or unsubstituted divalent aromatic heterocyclic group, and Ar ³ represents a substituted or unsubstituted monovalent aromatic group. Group hydrocarbon group or a substituted or unsubstituted monovalent aromatic heterocyclic group, X ¹ is any of a direct bond, O, S, ═C (R ³ ) R ⁴ , and ═Si (R ⁵ ) R ⁶ Wherein R ^{3 to} R ⁶ are any one of a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, and a substituted or unsubstituted monovalent aromatic hydrocarbon group. ]
[However, the substitution in the general formula [1] and the general formula [2] is a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent Substituted with any of aromatic heterocyclic group, halogen atom, cyano group, alkoxyl group, aryloxy group, alkylthio group, arylthio group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group Is Rukoto. ] Ar ¹ is an organic electroluminescence element material according to claim 1, wherein the unsubstituted 3-perylenyl group. 3. The organic electroluminescent element material according to claim 1, wherein R ¹ and R ² are both monovalent organic residues represented by the general formula [2]. The organic electroluminescent element material according to any one of claims 1 to 3 , wherein X ¹ is a direct bond. 5. An organic electroluminescence device comprising a single layer or a multilayer organic layer formed between a pair of electrodes comprising an anode and a cathode, wherein at least one layer contains the material for an organic electroluminescence device according to any one of claims 1 to 4. An organic electroluminescence device. In the organic electroluminescent device having at least a layer of light-emitting layer between a pair of electrodes consisting of an anode and a cathode, a layer emitting layer containing claims 1 to 4 The material for organic electroluminescence devices according to any one An organic electroluminescence device. The organic electroluminescence device according to claim 6, further comprising at least one electron injection layer formed between the light emitting layer and the cathode.