JP2002363550A - Material for organic electroluminescent element, and electroluminescent element made by using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic EL element which exhibits a good luminescent color, a high luminous intensity and a high luminous efficiency and has a long life, and a material which is used for an organic EL element and can satisfy the requirements for those characteristics. SOLUTION: This material for an organic electroluminescent element comprises a compound represented by general formula [1] (wherein X and Y are each an electron attracting group; Z is an optionally substituted 3-30C divalent aliphatic hydrocarbon group having at least two bridgehead carbon atoms; Ar<1> is an optionally substituted 4-30C divalent aromatic hydrocarbon group or aromatic heterocyclic group; R<1> and R<2> are each an optionally substituted 1-18C monovalent aliphatic hydrocarbon group; and X and Y, Ar<1> and R<1> , R<1> and R<2> , and R<2> and Ar<1> may be combined 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, high efficiency, and long life, 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. For example, 4H-pyran derivatives such as DCJTB described in JP-A-10-308281 are disclosed. And X. T. Tao et al., Appl. Phys. Let
t. No. 78, No. 3, pp. 279-281, 2001.
3- (dicyanomethylene)-described in the year issue
To the extent that 5,5-dimethyl-1- (4-dimethylamino-styryl) cyclohexene (DCDDC) is known.

[0005]

The light emitting materials for organic EL devices for obtaining red light emission described in the prior art still do not have sufficient light emission luminance, light emission efficiency and light emission color. However, it has a serious problem that the stability upon repeated use is poor. Therefore, there has been a demand for an organic EL device which exhibits a good red emission color, high emission luminance and luminous efficiency, has a longer life, and a material for an organic EL device which can satisfy the requirement.

[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]

Embedded image

Wherein X and Y are each an electron-withdrawing group, Z is a substituted or unsubstituted divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms and having at least 2 bridgehead carbons, Ar ¹ Is a substituted or unsubstituted divalent aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 30 carbon atoms, R ¹
And R ² are a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. X and Y, Ar ¹ and R ¹ ,
R ¹ and R ² , or R ² and Ar ¹ may be bonded to each other to form a ring. The present invention also relates to the material for an organic electroluminescence device, wherein X and Y are both cyano groups.

In the present invention, Z is represented by the following general formula [2]:
The material for an organic electroluminescence device described above, General formula [2]

[0011]

Embedded image

[Wherein, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. Z ¹ and Z ² are
It is a direct bond or a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and Z ¹ and Z ² are not simultaneously a direct bond. R ³ and R ⁴ , R ³ and Z ¹ , R ³
And Z ² , R ⁴ and Z ¹ , R ⁴ and Z ² , Z ¹ and Z ² may be bonded to each other to form a ring. Further, the present invention provides an organic electroluminescence device comprising a single or multilayer organic layer formed between a pair of electrodes consisting of an anode and a cathode, wherein at least one layer contains the organic electroluminescence device material. It relates to a certain organic electroluminescence element.

The present invention also relates to an organic electroluminescence device comprising at least one light-emitting layer formed between a pair of electrodes consisting of 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.

Further, 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.

[0015]

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].

First, X and Y in the general formula [1] each represent an electron withdrawing group, and X and Y may be bonded to each other to form a ring. Here, the electron withdrawing group means a group in which Hammett's substituent constant σ has a value larger than 0. Accordingly, examples of the electron-withdrawing groups for X and Y include a halogen atom, a cyano group, a 2-cyanoethenyl group, a 2,2-dicyanoethenyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl group. Group, carbamoyl group, 4-cyanophenyl group and the like, but the present invention is not limited to these.

In the above, examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the acyl group include acetyl, propionyl, pivaloyl, cyclohexylcarbonyl, benzoyl, toluoyl, anisoyl, cinnamoyl and the like.

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.

Other examples of the electron-withdrawing group include those in which X and Y are bonded to each other to form a ring, as shown below.

[0024]

Embedded image

As a combination of X and Y described above, X and Y are preferably an electron-withdrawing group selected from a cyano group, a 2,2-dicyanoethenyl group and a 4-cyanophenyl group. It is more preferable that each of them is a cyano group. This is because these groups, especially cyano groups, not only have a strong electron-withdrawing property, but also have high heat resistance and low chemical reactivity.

Next, Z in the general formula [1] will be described. Z represents a substituted or unsubstituted divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms and having at least two bridgehead carbons. In the present invention, the bridgehead carbon refers to a carbon contained in a bridged hydrocarbon such as a bicyclo ring and a tricyclo ring, which corresponds to a so-called bridge. For example, in bicyclo [2.1.0] heptane, carbon at positions 1 and 4. Z is 2 of 3 to 30 carbon atoms.
Monovalent and polycyclic aliphatic hydrocarbon groups,
It may have an unsaturated bond, may be branched, or may form a ring.

The substituents on these divalent aliphatic hydrocarbon groups include monovalent aliphatic hydrocarbon groups, aryl groups, halogen atoms, cyano groups, alkoxyl groups,
Aryloxy group, alkylthio group, arylthio group,
An aliphatic heterocyclic group, an aromatic heterocyclic group, a substituted amino group, and an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, and an arylsulfonyl described in the above examples of the X and Y electron-withdrawing groups. Group.

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, examples of the alkyl group include an alkyl group having 1 to 18 carbon atoms. Specific examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group and an octyl group. , A decyl group, a dodecyl group, a pentadecyl group, a linear alkyl group having 1 to 18 carbon atoms such as an octadecyl group, and an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a 2-ethylhexyl group, Examples include a branched alkyl group having 3 to 18 carbon atoms such as an isooctadecyl group.

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 aryl group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group,
4-xylyl group, p-cumenyl group, mesityl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 9-phenanthryl group, 1-acenaphthyl group, 2-azulenyl group, 1-pyrenyl group, 2- An aryl group having 6 to 18 carbon atoms such as a triphenylel group is exemplified.

Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom.

The alkoxyl group includes 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 a methylthio group, an ethylthio group, a tert-butylthio group, a hexylthio group, an octylthio group and an octadecylthio group.

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.

Examples of the aliphatic heterocyclic group include an aliphatic heterocyclic group having 3 to 18 carbon atoms such as a 2-pyrazolino group, a piperidino group, a morpholino group and a 2-morpholinyl group.

Examples of the aromatic heterocyclic group include 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group and 2-furyl group. 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
-An aromatic heterocyclic group having 3 to 18 carbon atoms such as -benzofuryl group, 2-benzothienyl group, N-indolyl group, N-carbazolyl group and N-acridinyl group.

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.

Z is preferably an aliphatic hydrocarbon group which is not conjugated to the unsaturated double bond to which X and Y bind. The reason is as follows. T. Tao et al., App
l. Phys. Lett. No. 78, No. 3, 279
, Page 281 issued in 2001, when used as a luminescent material, Z is represented by the general formula [1]
When conjugated to the unsaturated double bond bonded to X and Y in Z, Z acts as an electron donating group for the unsaturated double bond bonded to X and Y, so that two charge transfer paths are formed in one molecule. This is because there is a concern that the emission wavelength range may be broadened.

For example, Z is preferably an aliphatic hydrocarbon group represented by the general formula [2]. Here, R ³ and R ⁴ represent a hydrogen atom or a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. Is the same as the above-described monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms in the substituent of Z, and the substituent referred to herein is the same as the substituent of Z. is there.

Here, Z ¹ and Z ² represent a direct bond or a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. 2
Examples of the valent aliphatic hydrocarbon group include an alkylene group having 1 to 18 carbon atoms such as a methylene group, a dimethylene group, a trimethylene group, a propylene group, and an ethylethylene group. The substituent herein has the same meaning as the substituent for Z. R ³ and R ⁴ , R ³ and Z ¹ , R ³ and Z ² , R ⁴ and Z ¹ , R ⁴ and Z ² , Z ¹ and Z ² may be bonded to each other to form a ring. good. Hereinafter, specific examples of Z ¹ and Z ² are shown (however,
Me represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0045]

Embedded image

[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

[0050]

Embedded image

[0051]

Embedded image

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 a 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.

Next, R ¹ and R ² in the general formula [1] will be described. R ¹ and R ² represent a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. The substituent herein has the same meaning as the substituent in Z, and two or more substituents may be bonded to each other to form a ring. The term “unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms” used herein has the same meaning as the monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms in the substituent of Z. Specific examples include linear and branched alkyl groups having 1 to 18 carbon atoms, alkenyl groups having 2 to 18 carbon atoms, alkynyl groups having 2 to 18 carbon atoms, and cycloalkyl groups having 3 to 18 carbon atoms.

As described above, since the organic electroluminescent device material of the present invention has a three-dimensionally umbrella structure, the association between molecules is suppressed, and the organic electroluminescent device is preferably used for organic EL devices. It is thought that the phenomenon that does not occur is unlikely to occur. The material for an organic electroluminescence device of the present invention has a molecular weight of 10
Those having a value of 00 or less are preferable. The reason for this is that if the molecular weight is too large, there is a concern that the vapor deposition property at the time of producing the element is deteriorated. So, as such,
In the general formula [1], Z is an unsubstituted divalent aliphatic hydrocarbon group having 3 to 10 carbon atoms having at least two or more bridgehead carbons, and an unsubstituted divalent aromatic having 4 to 10 carbon atoms in Ar ^1. Preferably, the aromatic hydrocarbon group or the aromatic heterocyclic group, and R ¹ and R ² are an unsubstituted monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. R ³ and R ⁴ are each a hydrogen atom or an unsubstituted monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and Z ¹ and Z ²
Is preferably a direct bond or an unsubstituted divalent aliphatic hydrocarbon group having 1 to 4 carbon atoms.

Table 1 shows typical examples of compounds that can be used as the material for an organic EL device of the present invention.
The present invention is by no means limited to these (however, in Table 1, Me represents a methyl group and Ph represents a phenyl group). Table 1

[0059]

[Table 1]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

Incidentally, 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 made of a light emitting 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 has 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, particularly effective hole injecting materials include aromatic tertiary amine derivatives and 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 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, fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxadioxide Azole, thiadiazole, tetrazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane,
Anthrone and the like and their derivatives are mentioned. Further, an inorganic / organic composite material obtained by doping a metal such as cesium into bathophenanthroline (for example, Proceedings of the Society of Polymer Science, No. 50
Vol. 4, No. 4, p. 660, published in 2001) are also examples of electron injection materials, but the present invention is not limited thereto.

Among the above electron injecting materials, particularly effective electron injecting 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]

[0082]

Embedded image

[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 substituent for 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 substituent for 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-hydroxyquinolinate) (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, preferable metal complex compounds include lithium 8-hydroxyquinolinate, bis (8-hydroxyquinolinato) zinc, 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]
Quinolinato) zinc and the like.

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, examples of the host material 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 hole-transporting material such as a stilbene derivative, a butadiene derivative, a benzidine-type triphenylamine derivative, a styrylamine-type triphenylamine derivative, a diaminoanthracene-type triphenylamine derivative, or a diaminophenanthrene-type triphenylamine derivative;
And conductive polymer materials such as polyvinyl carbazole and polysilane.

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 L element material include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenyl Butadiene, 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 the like 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 the other light emitting materials and doping materials but also the above-described hole injecting material may be used. 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, a material having a work function of more than 4 eV is 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.

Further, as the conductive material used for the cathode of the organic EL device of the present invention, those having a work function of less than 4 eV are suitable, such as magnesium, calcium, tin, lead, and 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 of 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 forming method, each layer forms a thin film 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 against 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 maximum luminous brightness. In addition, the present organic EL device is very stable against heat and current,
Furthermore, emission luminance that can be practically used can be obtained with a low driving voltage, so that deterioration, which has been a major problem up to now, can be significantly reduced. Therefore, the present organic EL device is applied to a flat panel display such as a wall-mounted television or a flat illuminator, and further to a light source such as a copying machine or a printer, a light source such as a liquid crystal display or an instrument, a display board, or a sign lamp. Can be considered.

[0099]

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 (1) 4-Methylbicyclo [3.1.0] hex-3-en-2-one in 100 ml of dimethylformamide.
8 g (100 mmol), malonodinitrile 5.9 g
(90 mmol), piperidine 1.5 g, acetic acid 0.3
g 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 (90 mmol) was added.
l) 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 16.5 g of compound (1).
I got The structure of the compound (1) was confirmed by mass spectrum, NMR spectrum and elemental analysis. Synthesis Example 2 Synthesis method of compound (12) 4,4,7-Trimethylbicyclo [4.1.0] hept-3-ene-2 in 100 ml of dimethylformamide
1-3.5 g (100 mmol) of -one, 5.9 g (90 mmol) of malonodinitrile, 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. After heating and stirring at 80 ° C for 1 hour,
13.4 g of 4-dimethylaminobenzaldehyde (90
mmol), and the mixture was further heated and stirred at 80 ° C. for 1 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 give compound (12) 1
9.2 g were obtained. Mass spectrum, NMR spectrum,
The structure of the compound (12) was confirmed by elemental analysis. Synthesis Example 3 Synthesis method of compound (15) Verbenone (V) was added to 100 ml of dimethylformamide.
13.5 g (100 mmol) of erbenone, 5.9 g (90 mmol) of malonodinitrile, 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, 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. 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 21.3 g of compound (15). Mass spectrum, NM
The structure of compound (15) was confirmed by R spectrum and elemental analysis. Synthesis Example 4 Method for synthesizing compound (31) Verbenone (V) was added to 100 ml of dimethylformamide.
13.5 g (100 mmol) of erbenone, 5.9 g (90 mmol) of malonodinitrile, 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, 4-diethylaminobenzaldehyde 1
6.0 g (90 mmol) were added, and further at 80 ° C. for 1 hour.
The mixture was heated and stirred for an 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 22.3 g of compound (31). Mass spectrum, NM
The structure of compound (31) was confirmed by R 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.

[0101]

Embedded image

(DCJTB)

[0103]

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 device are as follows: light emission luminance at a DC voltage of 10 V: 76 (cd / m ² ); maximum light emission luminance: 920 (cd / m ² )
/ M ^2), the red light-emission efficiency 0.43 (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 a light emission luminance of 0.9 (c) at a DC voltage of 7 V.
d / m ² ) and a maximum emission luminance of 47 (cd / m ² ) was obtained.

Comparative Example 1 DC instead of compound (12) was used as an electron-injection type light-emitting layer.
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 carbazole (PVK) were added at a weight ratio of 1: 1 to 1,2 on a washed glass plate with ITO electrodes.
-Dissolved in dichloroethane, and a hole injection layer having a thickness of 50 nm was obtained by a spin coating method. Next, a mixture of the compound (15) in Table 1 and a tris (8-hydroxyquinolinato) aluminum complex (Alq3) having a weight ratio of 1: 100 was deposited to form an electron-injection type light-emitting layer having a thickness of 60 nm. And one more magnesium and silver
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. The electron-injection type light emitting layer was deposited in a vacuum of 2 × 10 ⁻⁶ Torr at a substrate temperature of room temperature. This device emits light at a DC voltage of 7V.
3 (cd / m ² ), maximum emission luminance 8500 (cd / m ² )
m ² ), and red luminescence with a maximum luminous efficiency of 2.2 (lm / W) was obtained.

Comparative Example 2 DCDDC used in Comparative Example 1 in place of compound (15)
An organic EL device was obtained in the same manner as in Example 3 except that the above was used. This device has an emission luminance of 1.0 at a DC voltage of 7 V.
(Cd / m ² ), maximum emission luminance 5500 (cd / m ² ),
Although red light emission with a maximum light emission efficiency of 1.6 (lm / W) was obtained, it is clear that the light emission luminance and efficiency were inferior to those of Example 3.

Example 4 A compound (2) shown in Table 1 was dissolved in methylene chloride on a washed glass plate provided with an ITO electrode, and a 50 nm-thick hole injection type light emitting layer was obtained by spin coating. 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 3.7 (cd / m ² ) at a DC voltage of 8 V and a maximum light emission luminance of 8500 (cd / m ² ).
m ² ) and red light emission with a luminous efficiency of 1.9 (lm / W) was obtained.

Example 5 A compound (5) shown in Table 1 was vacuum-deposited on a washed glass plate with an ITO electrode to obtain a hole injection type luminescent layer having a thickness of 50 nm. 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, and magnesium and silver were further added thereto in 10: An electrode having a thickness of 100 nm was formed from the alloy mixed at 1 (weight ratio) 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 4.5 (cd / m ² ) at a DC voltage of 8 V and a maximum light emission luminance of 930.
Red light emission was obtained at 0 (cd / m ² ) and luminous efficiency of 2.3 (lm / W).

Example 6 TPD was vacuum-deposited on a washed 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 4200 (cd / m ² ) at a DC voltage of 10 V.

Example 7 TPD was vacuum-deposited on a washed glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 40 nm. Then, Table 1
(19) 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 7400 (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 27900 (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. 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 9000 (cd / m ² ) or more were exhibited.
Table 2

[0114]

[Table 2]

Example 31 α-NPD was vacuum-deposited on a cleaned glass plate with an ITO electrode to obtain a hole injection layer having a thickness of 20 nm. Then
The compound (4) 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 (Li
F) is 0.5 nm, and aluminum (Al) is 20
An electrode was formed by 0 nm vacuum evaporation 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 6000 (cd / m ² ) at a DC voltage of 10 V and a maximum light emission luminance of 3300.
0 (cd / m ² ) and luminescence efficiency of 2.3 (lm / W) were obtained.

Example 32 Compound (1) and compound (35) shown in Table 1 were used as a light emitting layer.
A thin film having a thickness of 30 nm deposited at a weight ratio of 1: 1 is provided.
An organic EL device was fabricated in the same manner as in Example 8 except that
did. This device has an emission luminance of 138 at a DC voltage of 12 V.
00 (cd / m ^Two) Maximum emission luminance 34400 (cd /
m^Two), Red light emission with a luminous efficiency of 2.3 (lm / W) was obtained.
Was.

Example 33 As a light emitting layer, a compound (16) 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 an emission luminance of 15700 (cd / m ² ) at a DC voltage of 12 V and a maximum emission luminance of 38.
Red light emission having a luminance of 500 (cd / m ² ) and a luminous efficiency of 2.7 (lm / W) was obtained.

Example 34 The compound (21) shown in Table 1 and a bis (2-methyl-5-methyl-8-hydroxyquinolinato) (phenolate) gallium complex were deposited as a light emitting layer 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 16400 (cd / m ² ) at a DC voltage of 12 V, a maximum emission luminance of 37600 (cd / m ² ), and an emission efficiency of 3.1.
(Lm / W) red light emission was obtained.

Example 35 As a light emitting layer, the compound (26) 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 17 at a DC voltage of 12 V.
200 (cd / m ^Two) Maximum luminance 36800 (cd /
m^Two), Red light emission with a luminous efficiency of 3.1 (lm / W) was obtained.
Was.

Example 36 As the light emitting layer, the compound (52) 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 1340 at a DC voltage of 12 V.
0 (cd / m ² ) maximum emission luminance 34800 (cd / m ² )
m ² ), and luminescence with a luminous efficiency of 2.9 (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 a light emitting layer by depositing the compound (53) 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
Luminance at 2V: 22,000 (cd / m ² ) Maximum luminous luminance: 43500 (cd / m ² ), luminous efficiency: 3.5 (lm / m ² )
Light emission of W) was obtained.

Example 38 As a light emitting layer, a thin film having a thickness of 30 nm in which the compound (58) shown in Table 1 and 4,4′-bis (β, β-diphenylvinyl) biphenyl were deposited at a weight ratio of 1:50 was provided. 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 17800 at a DC voltage of 12 V.
(Cd / m ² ) maximum emission luminance 31400 (cd / m ² ),
Light emission with a luminous efficiency of 2.3 (lm / W) was obtained.

Example 39 α-NPD was vacuum-deposited on a cleaned 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 (62) in Table 1 was vacuum-deposited to form a second light-emitting layer having a thickness of 30 nm. Then, bis (2-methyl-8-hydroxyquinolinato) (phenolate) gallium complex was vacuum-deposited to form an electron injection layer having a thickness of 30 nm, and magnesium and silver were 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 11800 (cd) at a DC voltage of 12 V.
/ M ² ), a maximum light emission luminance of 34500 (cd / m ² ), and a light emission efficiency of 2.4 (lm / W).

Example 40 On a cleaned glass plate with ITO electrodes, 4, 4 ', 4 "
-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 (15) 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 device has an emission luminance of 147 at a DC voltage of 12 V.
00 (cd / m^Two), Maximum emission luminance 39900 (cd /
m^Two), Red light emission with a luminous efficiency of 3.4 (lm / W) was obtained.
Was.

Example 41 As a light emitting layer, the compound (31) 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 3.2 (cd / A). The half-life was 1200 hours when driven at a constant current with an emission luminance of 500 (cd / m ² ).

Comparative Example 3 A compound (31) was replaced with DCJTB except that
An organic EL device was manufactured in the same manner as in Example 41. This device has an emission luminance of 90 (cd /
a m ^2), the half-life when the constant current driving with emission luminance 500 (cd / m ²⁾ was 120 hours.

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 device has an emission luminance of 230 V at a DC voltage of 9 V.
(Cd / m ² ) and red light emission with a luminous efficiency of 3.4 (cd / A). The half-life was 1,400 hours when driven at a constant current with a light emission luminance of 500 (cd / m ² ).

Comparative Example 4 A compound was prepared in the same manner as in the above except that DCJTB was used instead of compound (46).
An organic EL device was manufactured in the same manner as in Example 42. This device has an emission luminance of 100 (cd / m) at a DC voltage of 9 V.
² ), and the half-life was 150 hours when driven at a constant current with an emission luminance of 500 (cd / m ² ).

Example 43 An organic EL device was manufactured 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 a light emission luminance of 340 (cd / m ² ) at a DC voltage of 9 V and a light emission efficiency of 3.6 (c
Red light emission of d / A) was obtained. In addition, a light emission luminance of 500
(Cd / m ² ), the half life is 12 when driven at a constant current.
00 hours.

As is clear from the examples described above, the organic EL device of the present invention achieves the improvement of the luminous efficiency, the luminous brightness and the long life, and the luminescent material, the doping material, It does not limit the hole injection material, the electron injection material, the sensitizer, the resin, the electrode material, and the like, and the element manufacturing method.

[0131]

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.

Claims (6)

[Claims] 1. A material for an organic electroluminescence device, which is a compound represented by the following general formula [1]. General formula [1] [In the formula, X and Y are each an electron-withdrawing group, Z is a substituted or unsubstituted divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms and having at least 2 bridgehead carbons, Ar
¹ is a substituted or unsubstituted divalent aromatic hydrocarbon group or aromatic heterocyclic group having 4 to 30 carbon atoms, R ¹ and R ²
Is a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. X and Y, Ar ¹ and R ¹ , R ¹ and R ² ,
R ² and Ar ¹ may combine with each other to form a ring. ] 2. The material for an organic electroluminescence device according to claim 1, wherein both X and Y are cyano groups. 3. The material for an organic electroluminescence device according to claim 1, wherein Z is represented by the following general formula [2]. General formula [2] [Wherein, R ³ and R ⁴ are each independently a hydrogen atom or a substituted or unsubstituted monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms. Z ¹ and Z ² are a direct bond or a substituted or unsubstituted divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and Z ¹ and Z ² are not simultaneously a direct bond. R ³ and R ⁴ , R ³ and Z ¹ , R ³ and Z ² , R ⁴ and Z ¹ , R ⁴ and Z ² , Z ¹ and Z ² may be bonded to each other to form a ring. ] 4. An organic electroluminescence device according to claim 1, wherein one or more organic layers are formed between a pair of electrodes comprising an anode and a cathode. An organic electroluminescent element which is a layer containing a material. 5. The organic electroluminescent device according to claim 1, wherein said at least one light emitting layer is formed between a pair of electrodes comprising an anode and a cathode. An organic electroluminescence device which is a layer containing: 6. The organic electroluminescence device according to claim 5, further comprising at least one electron injection layer formed between the light emitting layer and the cathode.