JP2002371271A - Organic electroluminescent device material and organic electroluminescent device using the same - Google Patents

Abstract

(57) [Problem] To provide an organic EL device exhibiting good luminescent color, high luminous brightness and luminous efficiency, and a material for an organic EL device capable of satisfying the same. A material for an organic electroluminescence device, which is a compound represented by the following general formula [1]. General formula [1] [Wherein, W is any one of a carbonyl group, a sulfinyl group, and a sulfonyl group, X is an organic residue having 1 to 18 carbon atoms,
Y is any one of a hydrogen atom, a halogen atom, and an organic residue having 1 to 18 carbon atoms, and Z is a substituted or unsubstituted divalent fat having 2 to 20 carbon atoms for forming a 5- to 7-membered ring. A group hydrocarbon group, Ar ¹ is a substituted or unsubstituted divalent aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 30 carbon atoms. X and Y may combine with each other to form a ring. ]

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for an organic electroluminescence (EL) device used for a flat light source and a display, and an organic EL device using the same. More specifically, the present invention relates to a material for an organic EL device having high luminance and high efficiency and capable of obtaining red light emission, and an organic EL device using the same.

[0002]

2. Description of the Related Art An EL device using an organic substance is expected to be used as an inexpensive, large-area, full-color display device of a solid light emitting type, and many developments have been made. Generally, an EL element includes a light-emitting layer and a pair of opposed electrodes sandwiching the light-emitting 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, and the electrons recombine with holes in the light emitting layer, and the energy level is changed to the conduction band. This is a phenomenon in which energy is emitted as light when returning to the valence band from.

[0003] Conventional organic EL devices have a higher driving voltage and lower luminous brightness and luminous efficiency than inorganic EL devices.
In addition, the characteristic deterioration was remarkable, and it had not been put to practical use.
2. Description of the Related Art In recent years, an organic EL in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less is laminated.
Devices have been reported and are of interest (Appl. Phys.
s. Lett. 51, p. 913, 1987). This method uses a metal chelate complex for a light emitting layer and an amine compound for a hole injection layer to obtain high-brightness green light emission.
(Cd / m ² ) and a maximum luminous efficiency of 1.5 (lm / W), which is close to the practical range.

[0004] Among organic EL devices, there are few reports on light emitting materials for organic EL devices for obtaining red light emission. T. Tao et al., Appl. Ph
ys. Lett. , No. 78, No. 3, 279-281
P., 2001, 3- (dicyanomethylene) -5,5-dimethyl-1- (4-dimethylamino-styryl) cyclohexene (DCDDC).

[0005]

The luminescent material for an organic EL device for obtaining red luminescence described in the prior art has a problem that it is difficult to obtain sufficient luminous luminance and luminous efficiency. Therefore, good red emission color, high emission brightness,
There has been a demand for an organic EL device exhibiting luminous efficiency and a material for an organic EL device capable of satisfying the same.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above problems in consideration of the above problems, and as a result, have reached the present invention.

That is, the present invention relates to a material for an organic electroluminescence device, which is a compound represented by the following general formula [1]. General formula [1]

[0008]

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Wherein W represents a carbonyl group, a sulfinyl group or a sulfonyl group, and X represents
18 represents an organic residue, Y represents a hydrogen atom, a halogen atom, or an organic residue having 1 to 18 carbon atoms;
Represents a substituted or unsubstituted divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms for forming a 5- to 7-membered ring;
¹ represents a substituted or unsubstituted divalent aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 30 carbon atoms. X and Y
May combine with each other to form a ring. The present invention also relates to the material for an organic electroluminescence device, wherein Z is the following general formula [2]. General formula [2]

[0010]

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[Wherein R¹~ R⁶Are each independently water
A hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms
A alkyl group, R¹And R^Two, R¹And R^Three, R¹And R^Four, R¹
And R^Five, R¹And R⁶, R^TwoAnd R^Three, R^TwoAnd R^Four, R^TwoAnd R^Five, R^Two
And R⁶, R^ThreeAnd R^Four, R^ThreeAnd R^Five, R ^ThreeAnd R⁶, R^FourAnd R^Five, R^Four
And R⁶, R^FiveAnd R⁶Are bonded to each other to form a ring
good. n is an integer of 0 or 1. In addition, the present invention relates to a method comprising the steps of:
Organic electro-electrode formed by forming one or more organic layers
In a luminescent element, at least one
Layer containing materials for electroluminescent devices
It relates to a certain organic electroluminescence element.

Further, the present invention provides an organic electroluminescence device comprising at least one light-emitting layer formed between a pair of electrodes comprising an anode and a cathode, wherein the light-emitting layer contains the above-mentioned material for an organic electroluminescence device. And an organic electroluminescence device.

[0013] The present invention further relates to the above organic electroluminescent device, wherein at least one electron injection layer is formed between the light emitting layer and the cathode.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, the material for an organic EL device of the present invention is characterized by being a compound represented by the general formula [1]. Here, W in the general formula [1] represents any of a carbonyl group, a sulfinyl group, and a sulfonyl group. When W is any of these groups, it is possible to secure the charge transfer path from the amino group bonded to Ar ¹ and the fluorescence. Among the above, the case where W is a carbonyl group is particularly preferred.

Next, X in the general formula [1] is a group having 1 carbon atom.
~ 18 organic residues. The organic residue having 1 to 18 carbon atoms here may be any organic residue that forms a stable bond with W. For example, a monovalent aliphatic hydrocarbon group,
Aromatic hydrocarbon group, aliphatic heterocyclic group, aromatic heterocyclic group,
Further examples include an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, a substituted amino group and the like.

Here, the monovalent aliphatic hydrocarbon group refers to a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms,
Such include alkyl, alkenyl,
Examples include an alkynyl group and a cycloalkyl group.

Accordingly, the alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, Examples thereof include an alkyl group having 1 to 18 carbon atoms such as an octyl group, a decyl group, a dodecyl group, a pentadecyl group, and an octadecyl group.

Further, as the alkenyl group, a vinyl group,
C2-C18 such as 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group, and 1-octadecenyl group An alkenyl group is exemplified.

The alkynyl group includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-octynyl, 1-decynyl, 1-decynyl, An alkynyl group having 2 to 18 carbon atoms such as an octadecynyl group is exemplified.

The cycloalkyl group includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl,
Examples thereof include a cycloalkyl group having 3 to 18 carbon atoms such as a cyclooctadecyl group.

Further, examples of the monovalent aromatic hydrocarbon group include monovalent monocyclic, condensed ring and ring-assembled hydrocarbon groups having 6 to 18 carbon atoms. Here, the monovalent monocyclic aromatic hydrocarbon group having 6 to 18 carbon atoms includes a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, a p-cumenyl group. And monovalent aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as a group and a mesityl group.

The monovalent fused ring hydrocarbon group includes
1-naphthyl group, 2-naphthyl group, 1-anthryl group,
2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, 1-acenaphthyl group,
Examples thereof include a monovalent condensed ring hydrocarbon group having 10 to 18 carbon atoms such as a 2-azulenyl group, a 1-pyrenyl group, and a 2-triphenylel group.

Further, as the monovalent ring-assembled hydrocarbon group,
Examples thereof include monovalent ring-assembled hydrocarbon groups having 12 to 18 carbon atoms, such as an o-biphenylyl group, an m-biphenylyl group, and a p-biphenylyl group.

As the monovalent aliphatic heterocyclic group, 2
-A monovalent aliphatic heterocyclic group having 3 to 18 carbon atoms such as a pyrazolino group, a piperidino group, a morpholino group and a 2-morpholinyl group.

As the monovalent aromatic heterocyclic group, 2
-Furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2 -Pyrazyl group, 2-oxazolyl group, 3-
Isoxazolyl group, 2-thiazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 3-pyrazolyl 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, 2-quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-
Examples thereof include a monovalent aromatic heterocyclic group having 3 to 18 carbon atoms such as an indolyl group, an N-carbazolyl group, and an N-acridinyl group.

The alkoxyl groups include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, te
Examples thereof include an alkoxyl group having 1 to 18 carbon atoms such as an rt-butoxy group, an octyloxy group, and an octadecyloxy group.

Examples of the aryloxy group include those having 6 to 6 carbon atoms such as phenoxy, 4-tert-butylphenoxy, 1-naphthyloxy, 2-naphthyloxy, 9-anthryloxy and 1-pyrenyloxy. 1
And 8 aryloxy groups.

Examples of the alkylthio group include alkylthio groups having 1 to 18 carbon atoms, such as methylthio, ethylthio, tert-butylthio, hexylthio, octylthio, and octadecylthio.

Examples of the arylthio group include arylthio groups having 6 to 18 carbon atoms, such as phenylthio, 2-methylphenylthio, 4-tert-butylphenylthio, and 1-pyrenylthio.

The substituted amino group includes N-methylamino group, N-ethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutylamino group, N-benzylamino group. Group, N, N-dibenzylamino group, N-phenylamino group, N-phenyl-
N-methylamino group, N, N-diphenylamino group,
N, N-bis (m-tolyl) amino group, N, N-bis (p-tolyl) amino group, N, N-bis (p-biphenylyl) amino group, bis [4- (4-methyl) biphenylyl] Amino group, Np-biphenylyl-N-phenylamino group, N-α-naphthyl-N-phenylamino group, N
And substituted amino groups having 1 to 18 carbon atoms, such as -β-naphthyl-N-phenylamino group and N-phenanthryl-N-phenylamino group.

Preferred examples of the organic residue having 1 to 18 carbon atoms as X in the general formula [1] include a monovalent aliphatic hydrocarbon group, an aromatic hydrocarbon group and a substituted amino group.

Next, Y in the general formula [1] is any one of a hydrogen atom, a halogen atom and an organic residue having 1 to 18 carbon atoms. Here, examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

The organic residue having 1 to 18 carbon atoms in Y has the same meaning as the organic residue having 1 to 18 carbon atoms in X, but is preferably an electron-withdrawing group. Here, the electron withdrawing group means a group in which Hammett's substituent constant σ has a value larger than 0. Therefore, preferred organic residues for Y include a cyano group, a 2-cyanoethenyl group,
2-dicyanoethenyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, 4-
Examples include a cyanophenyl group, but the present invention is not limited to these. X and Y may be combined with each other to form a ring. In this case, the ring formed is preferably electron-withdrawing.

In the above, the acyl group includes an acetyl group,
Propionyl group, pivaloyl group, cyclohexylcarbonyl group, benzoyl group, toluoyl group, anisoyl group,
A cinnamoyl group;

Further, as the alkoxycarbonyl group,
Examples include a methoxycarbonyl group, an ethoxycarbonyl group, and a benzyloxycarbonyl group.

Examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthyloxycarbonyl group.

Examples of the alkylsulfonyl group include a mesyl group, an ethylsulfonyl group and a propylsulfonyl group.

Examples of the arylsulfonyl group include a benzenesulfonyl group and a toluenesulfonyl group.

Next, Z in the general formula [1] will be described. Z has 2 to 20 carbon atoms for forming a 5- to 7-membered ring.
Represents a substituted or unsubstituted divalent aliphatic hydrocarbon group. Examples of such an aliphatic hydrocarbon group include, for example, 5
Examples thereof include a saturated or unsaturated divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms forming a 7-membered ring, which may be branched or form a ring.

As the substituents in these divalent aliphatic hydrocarbon groups, the monovalent aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and aliphatic heterocyclic groups described in the above examples of the organic residue of X are exemplified. , An aromatic heterocyclic group, further, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, a substituted amino group, a halogen atom, a cyano group, an acyl group described in the above examples of the organic residue of Y, Examples thereof include an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group.

Z is preferably an aliphatic hydrocarbon group which is not conjugated to the unsaturated double bond to which X is bonded. The reason is as follows. T. Tao et al., Appl. Phys
s. Lett. , No. 78, No. 3, 279-281
As described in the page, published in 2001, when used as a light-emitting material, when Z is conjugated to an unsaturated double bond bonded to X in the general formula [1], Z becomes X To act as an electron donating group for the unsaturated double bond
This is because two charge transfer paths are generated in one molecule, and there is a concern that the emission wavelength range is broadened.

For example, Z is preferably an aliphatic hydrocarbon group represented by the general formula [2]. R ^{1 to} R ⁶ in the general formula [2] are each independently a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 18 carbon atoms. Here, the unsubstituted alkyl group having 1 to 18 carbon atoms means
It has the same meaning as the above-mentioned alkyl group having 1 to 18 carbon atoms in X. As the substituent, a monovalent aromatic hydrocarbon group, an aliphatic heterocyclic group,
In addition to the aromatic heterocyclic group, an alkoxyl group, an aryloxy group, an alkylthio group, an arylthio group, and a substituted amino group, the halogen atom, cyano group, acyl group, and alkoxy group described in the example of the organic residue of Y described above. Examples include a carbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group.

R ¹ and R ² , R ¹ and R ³ , R ¹ and R ⁴ , R
¹ and R ⁵ , R ¹ and R ⁶ , R ² and R ³ , R ² and R ⁴ , R ² and R ⁵ , R
² and R ⁶ , R ³ and R ⁴ , R ³ and R ⁵ , R ³ and R ⁶ , R ⁴ and R ⁵ , R
⁴ and R ⁶ , and R ⁵ and R ⁶ may combine with each other to form a ring. When Z is a group represented by the general formula [2], it forms a 5- or 6-membered ring, and forms an unsaturated double bond conjugated to an unsaturated double bond directly bonded to W and Y. Is particularly preferred because charge transfer from an amino group bonded to Ar ¹ easily occurs. Hereinafter, specific examples of the general formula [2] will be shown.

[0044]

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[0045]

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[0046]

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Next, Ar ¹ in the general formula [1] will be described. Ar ¹ represents a substituted or unsubstituted divalent aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 30 carbon atoms. The substituent herein has the same meaning as the substituent for Z, and two or more substituents may be bonded to each other to form a ring.

Here, the divalent aromatic hydrocarbon group means a divalent monocyclic or condensed ring or ring-assembled aromatic hydrocarbon group, such as a phenylene group, a naphthylene group, an anthrylene group or a biphenylene group. And a divalent aromatic hydrocarbon group having 6 to 30 carbon atoms.

The divalent aromatic heterocyclic group means a divalent monocyclic or condensed ring or a ring-assembled aromatic heterocyclic group, for example, a 2,5-furylene group, a 2,5-thienylene group. ,
Examples thereof include a divalent aromatic heterocyclic group having 4 to 30 carbon atoms, such as a 2,4-pyridylene group and a 2,6-quinolylene group.

Of the above-mentioned divalent aromatic hydrocarbon groups or aromatic heterocyclic groups in Ar ¹ , preferred are divalent C 6 -C 12 divalent groups such as phenylene, naphthylene and biphenylene. And aromatic hydrocarbon groups.

Table 1 shows typical examples of the compounds which can be used as the material for an organic EL device of the present invention.
The present invention is not at all limited to these (however, in Table 1, Me represents a methyl group, Et represents an ethyl group,
Ph represents a phenyl group).

[0052]

[Table 1]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

The organic EL device is a device in which one or more organic layers are formed between an anode and a cathode. Here, the single-layer organic EL device is formed of a luminescent material between the anode and the cathode. It has a light emitting layer. On the other hand, the multilayer organic EL device includes (anode / hole injection layer / light-emitting layer / cathode), (anode /
This is an organic EL device having a multilayer structure such as a light-emitting layer / electron injection layer / cathode and an anode / hole injection layer / light-emitting layer / electron injection layer / cathode. The material for an organic EL device of the present invention can be used for 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 formed using the light emitting material for an organic EL device, a hole injection material or an electron for efficiently transporting holes injected from an anode or electrons injected from a cathode to the light emitting material. An injection material can be included.

Here, the hole injection material indicates an excellent hole injection effect on the light emitting layer or the light emitting material, and prevents the exciton generated in the light emitting layer from moving to the electron injection layer or the electron injection material. And a compound having excellent thin film forming properties. Examples of such hole injecting materials include phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole , Hydrazone, acylhydrazone, polyarylalkane, stilbene, butadiene,
Benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine and the like, and derivatives thereof, and polyvinyl carbazole,
Examples thereof include polysilane and conductive polymer, but the present invention is not limited to these.

Among the above hole injecting materials, a particularly effective hole injecting material is an aromatic tertiary amine derivative or a phthalocyanine derivative. 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 an oligomer or polymer having an aromatic tertiary amine skeleton. As the phthalocyanine (Pc) derivative, H
₂ Pc, CuPc, CoPc, NiPc, ZnPc, P
dPc, FePc, MnPc, ClAlPc, ClGa
Pc, ClInPc, ClSnPc, Cl ₂ SiPc,
(HO) AlPc, (HO) GaPc, VOPc, Ti
Examples include phthalocyanine derivatives such as OPc, MoOPc, and GaPc-O-GaPc, and naphthalocyanine derivatives. The above-described hole injecting materials can be further sensitized by adding an electron accepting material.

On the other hand, the electron injecting material has an excellent electron injecting effect on the light emitting layer or the light emitting material, and prevents the exciton generated in the light emitting layer from moving to the hole injecting layer or the hole injecting material. And a compound having excellent thin film forming properties.
Examples of such electron injecting materials include quinoline metal complexes, oxadiazoles, benzothiazole metal complexes, benzoxazole metal complexes, benzimidazole metal complexes, acetylacetone metal complexes, fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandiene Examples include oxides, oxadiazoles, thiadiazoles, tetrazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and derivatives thereof. In addition, an inorganic / organic composite material obtained by doping a metal such as cesium into bathophenanthroline (for example, Proceedings of the Society of Polymer Science, Vol. 50, No. 4, p. 660, 2
001) is also given as an example of the electron injection material, but the present invention is not limited to these.

Among the above 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, a compound represented by the following general formula [3] can be suitably used. General formula [3]

[0077]

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[Wherein Q ¹ and Q ² each independently represent a substituted or unsubstituted hydroxyquinoline derivative or a substituted or unsubstituted hydroxybenzoquinoline derivative, and L represents a halogen atom, a substituted or unsubstituted An alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aromatic heterocyclic group, -OR (R is a hydrogen atom, a substituted or unsubstituted alkyl group, or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aromatic heterocyclic group), -. O-Ga- Q 3 (Q 4) (Q 3 and Q ⁴ Is
It has the same meaning as Q ¹ and Q ² . ) Represents a ligand represented by Here, general formula [3] will be described. Q ^{1 to} Q ⁴ of the compound represented by the general formula [3] are a substituted or unsubstituted hydroxyquinoline derivative or a substituted or unsubstituted hydroxybenzoquinoline derivative. The substituent herein has the same meaning as the organic residue having 1 to 18 carbon atoms in Z in the general formula [1].

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 herein has the same meaning as the organic residue having 1 to 18 carbon atoms in Z in the general formula [1]. 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.

Accordingly, specific examples of the compound represented by the general formula [3] include bis (2-methyl-8-hydroxyquinolinato) (1-naphtholate) gallium complex,
Bis (2-methyl-8-hydroxyquinolinate) (2
-Naphtholate) gallium complex, bis (2-methyl-8)
-Hydroxyquinolinato) (phenolate) gallium complex, bis (2-methyl-8-hydroxyquinolinato) (4-cyano-1-naphtholate) gallium complex,
Bis (2,4-dimethyl-8-hydroxyquinolinato) (1-naphtholate) gallium complex, bis (2,5
-Dimethyl-8-hydroxyquinolinato) (2-naphtholate) gallium complex, bis (2-methyl-5-phenyl-8-hydroxyquinolinato) (phenolate)
Gallium complex, bis (2-methyl-5-cyano-8-hydroxyquinolinato) (4-cyano-1-naphtholate) gallium complex, bis (2-methyl-8-hydroxyquinolinato) chlorogallium complex, bis (2-methyl-8-hydroxyquinolinate) (o-cresolate)
Although a gallium complex etc. are mentioned, the present invention is not limited to these. The compound represented by the general formula [3] can be synthesized by the method described in JP-A-10-88,121.

Among the electron injecting materials usable in the present invention, preferred metal complex compounds include lithium 8-hydroxyquinolinate, zinc bis (8-hydroxyquinolinate), and bis (8-hydroxyquinolinate). )
Copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, Bis (10-hydroxybenzo [h] quinolinate) beryllium, bis (10-hydroxybenzo [h]
Quinolinate) zinc and nickel acetylacetonate.

Among the electron-injecting materials usable in the present invention, preferable nitrogen-containing five-membered derivatives include oxazole, thiazole, oxadiazole, thiadiazole and triazole derivatives.
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 and the like. The above-described electron injecting materials can be further sensitized by adding an electron donating material.

Further, the material for an organic EL device of the present invention can be used by doping in a light emitting layer. In this case, the present organic EL device material is preferably contained in the range of 0.001 to 50% by weight, more preferably 0.01 to 10% by weight, based on the host material described below. More preferably, it is performed.

When the organic EL device material of the present invention is used as a doping material, host materials that can be used together include a quinoline metal complex, a benzoquinoline metal complex, a benzoxazole metal complex, a benzothiazole metal complex,
Benzimidazole metal complex, benzotriazole metal complex, imidazole derivative, oxadiazole derivative,
Electron transporting materials such as thiadiazole derivatives and triazole derivatives. Or a stilbene derivative, a butadiene derivative, a benzidine triphenylamine derivative, a styrylamine triphenylamine derivative, a diaminoanthracene triphenylamine derivative, a diaminophenanthrene triphenylamine derivative, 2,3,6,7,1
Examples thereof include a hole transporting material such as 0,11-hexaalkoxytriphenylene and a conductive polymer material such as polyvinylcarbazole and polysilane.

Further, in the light emitting layer of the present organic EL device, in addition to the material for the organic EL device 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 material for an organic EL device of the present invention may function as a host material in some cases. Organic E of the present invention
Other light-emitting materials and doping materials that can be used together with the material for the L element include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, 3,4,9,10-perylenetetracarbon. Acid tetraalkyl esters, perinones, phthaloperinones,
Naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran Thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compounds, quinacridone, rubrene, and derivatives thereof.

In the light emitting layer of the present organic EL device, in addition to the material for the organic EL device of the present invention, if necessary, not only other light emitting materials and doping materials but also the above-described hole injecting material Also, two or more kinds of electron injection materials can be used in combination. Further, each of the hole injection layer, the light emitting layer, and the electron injection layer may be formed in a layer structure of two or more layers.

Further, as the conductive material used for the anode of the organic EL device of the present invention, those having a work function larger than 4 eV are suitable.
Aluminum, vanadium, iron, cobalt, nickel,
Tungsten, silver, gold, platinum, palladium and the like, and alloys thereof, metal oxides such as tin oxide and indium oxide referred to as ITO substrates and NESA substrates, and organic conductive polymers such as polythiophene and polypyrrole can be given.

The conductive material used for the cathode of the organic EL device of the present invention is preferably a material having a work function of less than 4 eV, such as magnesium, calcium, tin, lead, or the like. Examples include titanium, yttrium, lithium, lithium fluoride, ruthenium, manganese, and the like, and alloys thereof. Here, alloys include magnesium / silver, magnesium / indium,
Representative examples include lithium / aluminum, but are not limited thereto. The alloy ratio is
Since the temperature can be controlled by the heating temperature, atmosphere, and degree of vacuum during preparation, an alloy having an appropriate ratio can be prepared. These anodes and cathodes may be formed of two or more layers if necessary.

In order for the organic EL device of the present invention to emit light efficiently, it is desirable that the material constituting the device is sufficiently transparent in the emission wavelength region of the device, and that the substrate is also transparent. The transparent electrode can be formed by a method such as vapor deposition or sputtering using the above conductive material. In particular, the electrode on the light emitting surface has a light transmittance of 1
Desirably, it is 0% or more. The substrate is not particularly limited as long as it has mechanical and thermal strength and is transparent. For example, a glass substrate and a transparent polymer such as polyethylene, polyethersulfone, and polypropylene are recommended.

The method for forming each layer of the organic EL device of the present invention includes vacuum deposition, sputtering, plasma,
Either a dry film forming method such as ion plating or a wet film forming method such as spin coating, dipping, or flow coating can be applied.
The thickness of each layer is not particularly limited, but needs to be set to an appropriate thickness. If the film thickness is too large, a large applied voltage is required to obtain a constant light output, and the efficiency is reduced. Conversely, if the film thickness is too small, pinholes and the like occur, making it difficult to obtain sufficient light emission luminance even when an electric field is applied.
Therefore, the normal film thickness is suitably in the range of 1 nm to 1 μm, but is more preferably in the range of 10 nm to 0.2 μm.

In the case of the wet film formation method, each layer is formed by dissolving or dispersing a material constituting the layer 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 of the wet film forming methods, a suitable polymer or additive may be used for improving film forming properties, preventing pinholes in the film, and the like. Examples of such a polymer 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-vinyl carbazole and polysilane. And conductive polymers such as polythiophene and polypyrrole. In addition, examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer. When the material of the present invention is formed by a wet method, since the affinity between the molecules of each compound is good, even if the compound alone has a high cohesiveness and the film tends to be non-uniform, it may be mixed with a derivative having a low cohesiveness. A good film can be obtained by using the material.

In order to improve the stability of the organic EL device obtained according to the present invention with respect to temperature, humidity, atmosphere, etc.,
Further, a protective layer may be provided on the surface of the device, or the entire device may be covered with silicone oil, polymer, or the like.

As described above, the organic EL device manufactured using the present organic EL device material can improve characteristics such as luminous efficiency and luminous brightness. In addition, the present organic EL device is extremely stable against heat and current, and furthermore, can obtain a practically usable emission luminance at a low driving voltage, so that the deterioration which has been a major problem until now is greatly reduced. It is possible to lower. Therefore, the present organic EL device
As a flat panel display such as a wall-mounted TV or a flat illuminator, furthermore, a light source such as a copying machine or a printer,
It can be applied to light sources such as liquid crystal displays and instruments, display boards, and marker lights.

[0094]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples. First, a synthesis example of the material for an organic EL device of the present invention will be described prior to the examples. Synthesis Example 1 Synthesis method of compound (11) In 100 ml of dimethylformamide, 9.6 g (100 mmol) of 3-methylcyclopent-2-enone, 11.9 g (90 mmol) of dimethyl malonate, 1.5 g of piperidine, and 0.1 g of acetic acid. 3 g and 0.2 g of acetic anhydride were added,
Stirred at room temperature for 1 hour. Subsequently, after heating and stirring at 80 ° C. for 1 hour, 4-dimethylaminobenzaldehyde 1
3.4 g (90 mmol) were added, and further at 80 ° C. for 1 hour.
The mixture was heated and stirred for an hour. The mixture was concentrated under reduced pressure, 3 ml of concentrated hydrochloric acid and 150 ml of water were added to the residue, and the resulting precipitate was purified by column chromatography to obtain 20.6 g of compound (11). Mass spectrum, NM
The structure of compound (11) was confirmed by R spectrum and elemental analysis. Synthesis Example 2 Synthesis method of compound (45) In 100 ml of dimethylformamide, 9.6 g (100 mmol) of 3-methylcyclopent-2-enone was added.
13.1 g (90 mmol) of 1,3-indandione,
Piperidine 1.5 g, acetic acid 0.3 g, acetic anhydride 0.2 g
Was added and stirred at room temperature for 1 hour. After heating and stirring at 80 ° C. for 1 hour, 13.4 g (90 mmol) of 4-dimethylaminobenzaldehyde was added.
The mixture was heated and stirred at ℃ for 1 hour. This mixture was concentrated under reduced pressure, and 3 ml of concentrated hydrochloric acid and 150 ml of water were added to the residue. The resulting precipitate was purified by column chromatography to obtain 21.6 g of compound (45). The compound (4) was analyzed by mass spectrum, NMR spectrum and elemental analysis.
The structure of 5) was confirmed. Synthesis Example 3 Synthesis method of compound (47) 9.6 g (100 mmol) of 3-methylcyclopent-2-enone in 100 ml of dimethylformamide, 3
-14.5 g (90 mmol) of ethyl rhodanine, 1.5 g of piperidine, 0.3 g of acetic acid and 0.2 g of acetic anhydride were added, and the mixture was stirred at room temperature for 1 hour. Subsequently, after heating and stirring at 80 ° C. for 1 hour, 13.4 g (90 mmol) of 4-dimethylaminobenzaldehyde was added, and the mixture was further heated and stirred at 80 ° C. for 1 hour. The mixture was concentrated under reduced pressure, and 3 ml of concentrated hydrochloric acid and 150 ml of water were added to the residue. The resulting precipitate was purified by column chromatography to obtain 20.1 g of compound (47). The compound (4) was analyzed by mass spectrum, NMR spectrum and elemental analysis.
The structure of 7) was confirmed. Synthesis Example 4 Synthesis method of compound (48) In 100 ml of dimethylformamide, 9.6 g (100 mmol) of 3-methylcyclopent-2-enone,
14.1 g of 1,3-diethylhydantoin (90 mmol
l), 1.5 g of piperidine, 0.3 g of acetic acid and 0.2 g of acetic anhydride were added, and the mixture was stirred at room temperature for 1 hour. Continue 8
After heating and stirring at 0 ° C. for 1 hour, 13.4 g (90 mmol) of 4-dimethylaminobenzaldehyde was added, and the mixture was further heated and stirred at 80 ° C. for 1 hour. The mixture was concentrated under reduced pressure, and 3 ml of concentrated hydrochloric acid and 150 ml of water were added to the residue. The resulting precipitate was purified by column chromatography to obtain 22.9 g of compound (48). The structure of Compound (48) was confirmed by mass spectrum, NMR spectrum and elemental analysis. Synthesis Example 5 Synthesis method of compound (51) In 100 ml of dimethylformamide, 9.6 g (100 mmol) of 3-methylcyclopent-2-enone, 12.6 g (90 mmol) of dimedone, and 1.5 parts of piperidine.
g, 0.3 g of acetic acid and 0.2 g of acetic anhydride were added and stirred at room temperature for 1 hour. Subsequently, after heating and stirring at 80 ° C. for 1 hour, 13.4 g of 4-dimethylaminobenzaldehyde was added.
(90 mmol), and the mixture was further heated and stirred at 80 ° C. for 1 hour. The mixture was concentrated under reduced pressure, and concentrated hydrochloric acid was added to the residue.
The precipitate obtained by adding 150 ml of water and 150 ml of water was purified by column chromatography, and the compound (5
1) 20.6 g was obtained. The structure of the compound (51) was confirmed by mass spectrum, NMR spectrum and elemental analysis. Synthesis Example 6 Synthesis method of compound (75) Isophorone 1 in 100 ml of dimethylformamide
3.8 g (100 mmol), 12.6 g of dimedone (9
0 mmol), 1.5 g of piperidine, 0.3 g of acetic acid, and 0.2 g of acetic anhydride, and the mixture was stirred at room temperature for 1 hour. Subsequently, after heating and stirring at 80 ° C. for 1 hour, 13.4 g (90 mmol) of 4-dimethylaminobenzaldehyde was added, and the mixture was further heated and stirred at 80 ° C. for 1 hour. The mixture was concentrated under reduced pressure, and 3 ml of concentrated hydrochloric acid and 150 ml of water were added to the residue.
The resulting precipitate was purified by column chromatography to give 22.9 g of compound (75). The structure of the compound (75) was confirmed by mass spectrum, NMR spectrum and elemental analysis.

Hereinafter, examples using the compound of the present invention will be described. In this example, all mixing ratios are by weight unless otherwise specified. In addition, characteristics of an organic EL device having an electrode area of 2 mm × 2 mm were measured. For comparison, the following known materials were used.

[0096]

Embedded image

(DCDDC) Example 1 A compound (1) shown in Table 1 and 2,5-bis (1-naphthyl)-as a luminescent material were placed on a washed glass plate with an ITO electrode.
1,2,10: 1,3,4-oxadiazole, polycarbonate resin (Teijin Chemical: Panlite K-1300)
Was dissolved in tetrahydrofuran at a weight ratio of, and a light-emitting layer having a thickness of 100 nm was obtained by spin coating. An electrode having a thickness of 150 nm was formed thereon using an alloy in which magnesium and silver were 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: 65 (cd / m ² ); maximum light emission luminance: 810 (cd
/ M ^2), the red light-emission efficiency 0.42 (lm / W) was obtained.

Example 2 On a cleaned glass plate with ITO electrodes, N, N '-(3
-Methylphenyl) -N, N'-diphenyl-1,1 '
-Biphenyl-4,4'-diamine (TPD) and polyvinyl carbazole (PVK) in a 1: 1 weight ratio of 1,2
-Dissolved in dichloroethane, and a hole injection layer having a thickness of 50 nm was obtained by a spin coating method. Next, the compound (12) shown in Table 1 was vapor-deposited to form a 60-nm-thick electron-injection light-emitting layer, on which magnesium and silver were mixed at a ratio of 10: 1.
An electrode having a thickness of 100 nm was formed from the alloy mixed at a (weight ratio) to obtain an organic EL device. 2 × 1 electron injection luminescent layer
Vapor deposition was performed at a substrate temperature of room temperature in a vacuum of 0 ^-6 Torr. This device has an emission luminance of 0.6 (c) at a DC voltage of 7 V.
d / m ² ) and red light emission with a maximum emission luminance of 40 (cd / m ² ).

Comparative Example 1 DC was used as an electron-injection light emitting layer instead of compound (12).
Except for using DDC, the organic E was prepared in the same manner as in Example 2.
An L element was obtained. This device has a light emission luminance of 0.4 (cd / m ² ) at a DC voltage of 7 V and a maximum light emission luminance of 32 (cd / m ² ).
Although red light emission was obtained, it is clear that the light emission luminance was inferior to the result of Example 2.

Example 3 TPD and polyvinyl chloride were placed on a cleaned glass plate with ITO electrodes.
Nylcarbazole (PVK) was added at a weight ratio of 1: 1 to 1,2.
-Dissolved in dichloroethane and used for spin coating
A hole injection layer having a thickness of 50 nm was obtained. Then, in Table 1,
Compound (48) and tris (8-hydroxyquinoliner)
G) 1: 100 weight with aluminum complex (Alq3)
A mixture consisting of a quantity ratio is deposited and an electron injection type having a film thickness of 60 nm
A light-emitting layer is formed, and magnesium and silver are added thereon:
An electrode with a thickness of 100 nm made of an alloy mixed at 1 (weight ratio)
Thus, an organic EL device was obtained. Electron injection type light emitting layer is 2 ×
10 ^-6In a vacuum of Torr, the substrate is steamed at room temperature.
I wore it. This device has an emission luminance of 1.4 at a DC voltage of 7 V.
(Cd / m^Two), Maximum emission luminance 6900 (cd / m^Two),
Red light emission with a maximum luminous efficiency of 1.8 (lm / W) is obtained.
Was.

Comparative Example 2 Except that DCDDC was used instead of compound (48),
An organic EL device was obtained in the same manner as in Example 3. This element
Is an emission luminance of 1.0 (cd / m) at a DC voltage of 7 V. ^Two), The most
Large light emission luminance 5500 (cd / m^Two), Maximum luminous efficiency
6 (lm / W) red light emission was obtained.
It is clear that the light emission brightness and efficiency are inferior to the results.
You.

Example 4 A compound (9) shown in Table 1 was dissolved in methylene chloride on a washed glass plate with an ITO electrode, and a hole injection type light emitting layer having a thickness of 50 nm was obtained by a spin coating method. Then, bis (2-methyl-8-hydroxyquinolinate)
(1-Naphtholate) gallium complex was vacuum-deposited to form an electron injection layer having a thickness of 40 nm, on which an alloy obtained by mixing magnesium and silver at a weight ratio of 10: 1 was used.
An 0 nm electrode was formed to obtain an organic EL device. The electron injection layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. This device has a light emission luminance of 3.2 (cd / m ² ) at a DC voltage of 8 V and a maximum light emission luminance of 7200 (cd / m ² ).
m ² ) and red luminescence with a luminous efficiency of 1.7 (lm / W) was obtained.

Example 5 A compound (14) shown in Table 1 was dissolved in methylene chloride on a washed glass plate with an ITO electrode, and a hole injection type light emitting layer having a thickness of 50 nm was obtained by a spin coating method. Then, a bis (2-methyl-8-hydroxyquinolinate) (p-cyanophenolate) gallium complex was 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 in which magnesium and silver were mixed at a weight ratio of 10: 1 to obtain an organic EL device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. This device has a light emission luminance of 3.3 (cd / m ² ) at a DC voltage of 8 V and a maximum light emission luminance of 7900 (c / m ² ).
d / m ² ) and red light emission with a luminous efficiency of 1.9 (lm / W) was obtained.

Example 6 TPD was vacuum-deposited on a cleaned glass plate with ITO electrodes to obtain a 20-nm-thick hole injection layer. Then, Table 1
Was vapor-deposited to form a light-emitting layer having a thickness of 40 nm, and then Alq3 was vapor-deposited to obtain an electron-injection layer having a thickness of 30 nm. An electrode having a thickness of 200 nm was formed thereon using an alloy in which magnesium and silver were mixed at a weight ratio of 10: 1 to obtain an organic EL device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. This device emitted red light having a light emission luminance of 3500 (cd / m ² ) at a DC voltage of 10 V.

Example 7 TPD was vacuum-deposited on a cleaned glass plate with ITO electrodes to obtain a hole injection layer having a thickness of 40 nm. Then, Table 1
(42) and Alq3 were co-evaporated at a composition ratio of 1: 100 (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 that, magnesium and silver are mixed at a ratio of 10: 1 (weight ratio).
An electrode having a thickness of 200 nm was formed from the alloy mixed in the above step to obtain an organic EL device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. This device has a light emission luminance of 6500 (cd / m ² ) at a DC voltage of 12 V and a light emission luminance of 20 V
And emitted red light having a luminance of 25300 (cd / m ² ).

Examples 8 to 30 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum-deposited on a washed glass plate with an ITO electrode to form a film. A hole injection layer having a thickness of 30 nm was formed. Next, the compounds of Table 1 and Alq3 were co-evaporated at a composition ratio of 1: 100 (weight ratio), and the film thickness was 30 n.
m light emitting layers were obtained. Further, a bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium complex is vacuum-deposited to form an electron injection layer having a thickness of 30 nm, on which magnesium and silver are added at a ratio of 10: 1 (weight ratio). An electrode having a thickness of 100 nm was formed from the alloy mixed in (1) to obtain an organic EL device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. Table 2 shows the light emission characteristics of this device. All of the organic EL elements of this embodiment have a maximum emission luminance of 2
High luminance characteristics of 5000 (cd / m ² ) or more were exhibited.

[0107]

[Table 2]

Example 31 α-NPD was vacuum-deposited on a washed glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 20 nm. Then
Compound (12) in Table 1 was vacuum-deposited to form a light-emitting layer having a thickness of 40 nm, and then Alq3 was deposited to obtain an electron-injection layer having a thickness of 30 nm. First, lithium fluoride (L
iF) is 0.5 nm, and aluminum (Al) is 2 nm.
Electrodes were formed by vacuum evaporation of 00 nm to obtain an organic EL device. Each layer was deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. This device has a light emission luminance of 4900 (cd / m ² ) at a DC voltage of 10 V and a maximum light emission luminance of 298.
Light emission of 00 (cd / m ² ) and luminous efficiency of 2.1 (lm / W) was obtained.

Example 32 As the light emitting layer, the compound (30) and the compound (32) shown in Table 1 were used.
Was prepared in the same manner as in Example 8 except that a thin film having a thickness of 30 nm was formed by vapor-depositing a 1: 1 weight ratio. This device has an emission luminance of 10 at a DC voltage of 12 V.
500 (cd / m ² ) maximum emission luminance 30300 (cd / m ² )
m ² ) and red luminescence with a luminous efficiency of 2.2 (lm / W) was obtained.

Example 33 As a light-emitting layer, a compound (33) shown in Table 1 and a bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium complex were deposited at a weight ratio of 1:50 to a thickness of 30 n.
An organic EL device was produced in the same manner as in Example 8, except that a thin film of m was provided. This device has a light emission luminance of 11800 (cd / m ² ) at a DC voltage of 12 V and a maximum light emission luminance of 31.
Red light emission having a luminance of 600 (cd / m ² ) and a luminous efficiency of 2.2 (lm / W) was obtained.

Example 34 As a light emitting layer, the compound (36) shown in Table 1 and a bis (2-methyl-5-methyl-8-hydroxyquinolinate) (phenolate) gallium complex were deposited at a weight ratio of 1:10. An organic EL device was manufactured in the same manner as in Example 8, except that a thin film having a thickness of 30 nm was provided. This device has an emission luminance of 13100 (cd / m ² ) at a DC voltage of 12 V, a maximum emission luminance of 32100 (cd / m ² ), and an emission efficiency of 2.4.
(Lm / W) red light emission was obtained.

Example 35 As a light emitting layer, the compound (37) shown in Table 1 and α-NPD were used.
A thin film having a thickness of 30 nm was deposited at a weight ratio of 1:10.
An organic EL device was fabricated in the same manner as in Example 8 except that
Made. This device has an emission luminance of 13 V at a DC voltage of 12 V.
300 (cd / m ^Two) Maximum light emission luminance 31200 (cd /
m^Two), Red light emission with a luminous efficiency of 2.5 (lm / W) was obtained.
Was.

Example 36 As the light emitting layer, the compound (45) shown in Table 1 and 2, 3, 6,
7,10,11-hexamethoxytriphenylene:
An organic EL device was manufactured in the same manner as in Example 8, except that a thin film having a thickness of 30 nm deposited at a weight ratio of 10 was provided. This device has an emission luminance of 1060 at a DC voltage of 12 V.
0 (cd / m ² ) maximum emission luminance 31500 (cd / m ² )
m ² ) and red luminescence with a luminous efficiency of 2.6 (lm / W) was obtained.

Example 37 The same procedure as in Example 8 was carried out except that a thin film having a thickness of 30 nm was formed as the light emitting layer by depositing the compound (47) shown in Table 1 and N, N'-dimethylquinacridone at a weight ratio of 100: 1. An organic EL device was produced by the method described in the above. This element has a DC voltage of 1
Emission luminance at 2V 21900 (cd / m ²⁾ maximum radiance 35800 (cd / m ^2), luminous efficiency 2.7 (lm /
Light emission of W) was obtained.

Example 38 As the light-emitting layer, a thin film having a thickness of 30 nm was prepared by depositing the compound (49) shown in Table 1 and 4,4'-bis (β, β-diphenylvinyl) biphenyl at a weight ratio of 1:50. Except for the above, an organic EL device was produced in the same manner as in Example 8.
This device has an emission luminance of 13400 at a DC voltage of 12 V.
(Cd / m ² ) maximum emission luminance 26700 (cd / m ² ),
Light emission having a light emission efficiency of 2.1 (lm / W) was obtained.

Example 39 α-NPD was vacuum-deposited on a washed glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 40 nm. Next, the compound (1) in Table 1 was vacuum-deposited to form a first light-emitting layer having a thickness of 10 nm, and then the compound (53) 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-hydroxyquinolinato) (phenolate) gallium complex is vacuum-deposited to form an electron injection layer having a thickness of 30 nm, and magnesium and silver are further deposited on the electron injection layer.
An electrode having a thickness of 100 nm was formed from an alloy mixed at a ratio of 0: 1 (weight ratio) to obtain an organic EL device. Each layer is 10 ^-6 Torr
The film was deposited under the condition of room temperature and substrate temperature in a vacuum of r. This device has an emission luminance of 10100 (cd) at a DC voltage of 12 V.
/ M ² ), a maximum light emission luminance of 28300 (cd / m ² ), and a light emission efficiency of 2.1 (lm / W).

Example 40 4,4 ', 4 "was placed on a washed glass plate with ITO electrodes.
-Tris [N- (3-methylphenyl) -N-phenyl
[Amino] triphenylamine by vacuum evaporation to a film thickness of 60
nm of the first hole injection layer was obtained. Then, α-NPD is
By vacuum evaporation, a second hole injection layer having a thickness of 20 nm was obtained. Sa
Further, the compound (56) in Table 1 was vacuum-deposited to a film thickness of 10
nm emission layer, and Alq3 is vacuum-deposited
An electron injection layer having a thickness of 30 nm was formed. On top of that, Li
0.2 nm of F and then 150 nm of Al are vacuum deposited
Thus, an electrode was formed to obtain an organic EL device. Each layer is 1
0 ^-6Vapor deposition under the condition of substrate temperature and room temperature in Torr vacuum
did. This element has an emission luminance of 107 V at a DC voltage of 12 V.
00 (cd / m^Two), Maximum emission luminance 35800 (cd /
m^Two), Red light emission with luminous efficiency of 2.3 (lm / W) was obtained.
Was.

Example 41 As a light emitting layer, the compound (58) shown in Table 1 and Alq3 were used in a ratio of 1:
An organic EL device was manufactured in the same manner as in Example 40 except that a thin film having a thickness of 30 nm was deposited at a weight ratio of 100. This device has an emission luminance of 210 V at a DC voltage of 9 V.
(Cd / m ² ) and red luminescence with a luminous efficiency of 2.5 (cd / A) were obtained.

Example 42 4,4 ', 4 "-Tris [N- (3-methylphenyl)
An organic EL device was manufactured in the same manner as in Example 41 except that a hole injection layer of copper phthalocyanine having a thickness of 20 nm was provided instead of [-N-phenylamino] triphenylamine. This element has an emission luminance of 220 V at a DC voltage of 9 V.
(Cd / m ² ) and red luminescence with a luminous efficiency of 2.6 (cd / A).

Example 43 An organic EL device was fabricated in the same manner as in Example 41 except that a bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium complex was used instead of Alq3 as the electron injection layer. Produced. This device has an emission luminance of 290 (cd / m ² ) at a DC voltage of 9 V and an emission efficiency of 3.0 (c
Red light emission of d / A) was obtained.

As is clear from the examples described above, the organic EL device of the present invention achieves an improvement in luminous efficiency and luminous brightness, and is used together with a luminescent material, a doping material, and a hole injection material. , Electron injection material, sensitizer, resin,
It does not limit the electrode material and the like and the element manufacturing method.

[0122]

The organic EL device produced using the material for an organic EL device of the present invention emits red light, has higher luminous efficiency, higher luminance, and has a longer luminous life as compared with the prior art.
It can be suitably used as a flat panel display such as a wall-mounted television or a flat illuminator, so it can be applied to light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and sign lights. It is.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) H05B 33/14 H05B 33/14 B 33/22 33/22 BD

Claims (5)

[Claims] 1. A material for an organic electroluminescence device, which is a compound represented by the following general formula [1]. General formula [1] [Wherein, W represents a carbonyl group, a sulfinyl group, or a sulfonyl group, X represents an organic residue having 1 to 18 carbon atoms, and Y represents a hydrogen atom, a halogen atom, or
Represents an organic residue having 1 to 18 carbon atoms, Z represents a substituted or unsubstituted divalent aliphatic hydrocarbon group having 2 to 20 carbon atoms for forming a 5- to 7-membered ring, and Ar ¹ represents , Carbon number 4 ~
Represents 30 substituted or unsubstituted divalent aromatic hydrocarbon groups or aromatic heterocyclic groups. X and Y may combine with each other to form a ring. ] 2. The method according to claim 1, wherein Z is the following general formula [2].
The organic electroluminescent element according to claim 1,
Child material. General formula [2][Wherein, R¹~ R⁶Is independently a hydrogen atom or
A substituted or unsubstituted alkyl group having 1 to 18 carbon atoms
R¹And R^Two, R¹And R^Three, R¹And R^Four, R¹And R^Five, R¹When
R⁶, R^TwoAnd R^Three, R^TwoAnd R^Four, R^TwoAnd R^Five, R^TwoAnd R⁶, R^ThreeWhen
R^Four, R^ThreeAnd R^Five, R ^ThreeAnd R⁶, R^FourAnd R^Five, R^FourAnd R⁶, R^FiveWhen
R⁶May combine with each other to form a ring. n is
It is an integer of 0 or 1. ] 3. An organic electroluminescent device comprising one or more organic layers formed between a pair of electrodes comprising an anode and a cathode, wherein at least one layer comprises the material for an organic electroluminescent device according to claim 1 or 2. An organic electroluminescent element which is a layer containing. 4. An organic electroluminescence device comprising at least one light-emitting layer formed between a pair of electrodes comprising an anode and a cathode, wherein the light-emitting layer contains the material for an organic electroluminescence device according to claim 1 or 2. Organic electroluminescent element which is a layer to be formed. 5. The organic electroluminescence device according to claim 4, wherein at least one electron injection layer is formed between the light emitting layer and the cathode.