JPH1187066A - Organic electroluminescent element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve stability and durability, and prolong the light emitting lifetime by sandwiching at least one layer, which contains a specified compound of amino fluorene derivative, as a hole injection and transfer layer between a pair of electrodes. SOLUTION: A hole injection and transfer layer, an organic compound light emitting layer and an electron injection and transfer layer or the like is sandwiched between a positive electrode and a negative electrode so as to obtain an organic electroluminescent element. At this stage, at least one layer of each layer between both the electrodes is formed so as to contain at least one kind of compound expressed with a formula (in the formula, Ar1 -Ar4 mean a substituent or un-substituent aryl group, but at least one of Ar1 -Ar4 means a substituent or un-substituent naphthyl group, a substituent or un-substituent anthryl group, a substituent or un-substituent biphenyl group, and R1 , R2 mean a normal chained, branched, or cyclic alkyl group, a substituent or un-substituent aralkyl group). As a described compound included layer, a hole injection and transfer layer is desirable, and a light emitting layer can be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an organic electroluminescent device.

[0002]

2. Description of the Related Art Conventionally, an inorganic electroluminescent element has been used as a panel-type light source such as a backlight. However, driving the light emitting element requires a high AC voltage. Recently, an organic electroluminescent device (organic electroluminescent device: organic EL device) using an organic material as a light emitting material has been developed [Appl. Phys. Lett., 51 ,
913 (1987)]. The organic electroluminescent element has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode,
An exciton is generated by injecting electrons and holes into the thin film and recombining them, and emits light using light emitted when the exciton is deactivated. is there. The organic electroluminescent element can emit light at a low DC voltage of about several volts to several tens of volts, and various colors (for example, red, blue, and green) can be obtained by selecting the type of the fluorescent organic compound. ) Is possible. Organic electroluminescent devices having such features include various light emitting devices,
Application to display elements and the like is expected. However,
In general, organic electroluminescent devices have disadvantages such as poor stability and durability. As a hole injection transport material, 4,4′-bis [N-phenyl-N-
It has been proposed to use (3 "-methylphenyl) amino] biphenyl [Jpn. J. Appl. Phys., 27 , L2.
69 (1988)]. Further, as a hole injecting and transporting material, for example, a 9,9-dialkyl-2,7-bis (N, N-diphenylamino) fluorene derivative [eg, 9,9-dimethyl-2,7-bis (N, N -Diphenylamino) fluorene!
No. 25473). However, these organic electroluminescent elements also have disadvantages such as poor stability and durability. At present, further improved organic electroluminescent devices are desired.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electroluminescent device having improved stability and durability.

[0004]

Means for Solving the Problems The present inventors have made intensive studies on the organic electroluminescent device, and as a result, completed the present invention. That is, the present invention provides an organic electroluminescent device comprising at least one layer containing at least one compound represented by the general formula (1) (formula 2) between a pair of electrodes,

[0005]

Embedded image [In the formula, Ar _{1 to} Ar ₄ represent a substituted or unsubstituted aryl group (provided that at least one of Ar _{1 to} Ar ₄ is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, or a substituted Or represents an unsubstituted biphenyl group), and R ₁ and R ₂ represent a linear, branched or cyclic alkyl group or a substituted or unsubstituted aralkyl group.] A compound represented by the general formula (1) is contained. The organic electroluminescent device according to the above, wherein the layer is a hole injecting and transporting layer, the organic electroluminescent device according to the above or the above, further including a light emitting layer, between the pair of electrodes, the electron injecting and transporting layer, The organic electroluminescent device according to any one of the above-mentioned items, wherein

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The organic electroluminescent device of the present invention, between a pair of electrodes,
At least one compound represented by the general formula (1)
At least one layer containing the seeds is sandwiched.

[0007]

Embedded image [In the formula, Ar _{1 to} Ar ₄ represent a substituted or unsubstituted aryl group (provided that at least one of Ar _{1 to} Ar ₄ is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, or a substituted Or an unsubstituted biphenyl group), and R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, or a substituted or unsubstituted aralkyl group.

In the compound represented by the general formula (1),
Ar _{1 to} Ar ₄ represent a substituted or unsubstituted aryl group (provided that at least one of Ar _{1 to} Ar ₄ is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, or a substituted or unsubstituted Represents a biphenyl group). Note that the aryl group represents a carbocyclic aromatic group such as a phenyl group, a naphthyl group, and an anthryl group, and a heterocyclic aromatic group such as a furyl group, a thienyl group, and a pyridyl group. Ar _{1 to} Ar ₄ are preferably unsubstituted or, as a substituent, for example, a halogen atom,
A C6-C20 carbocyclic aromatic group which may be mono- or polysubstituted by an alkyl group having 1-10 carbon atoms, an alkoxy group having 1-10 carbon atoms, or an aryl group having 6-10 carbon atoms; Group or a heterocyclic aromatic group having a total of 4 to 20 carbon atoms, more preferably an unsubstituted or halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or carbon atom A carbocyclic aromatic group having a total of 6 to 20 carbon atoms, which may be mono- or polysubstituted with an aryl group having a number of 6 to 10, particularly preferably an unsubstituted or halogen atom, An alkyl group having 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a phenyl group having 6 to 20 carbon atoms which may be mono- or polysubstituted with an aryl group having 6 to 10 carbon atoms, Of the naphthyl group or the total Is an anthryl group of prime numbers 14 to 20.

Specific examples of Ar _{1 to} Ar ₄ include, for example, phenyl, 1-naphthyl, 2-naphthyl, 2
-Anthryl group, 9-anthryl group, 4-quinolyl group,
4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 3
-Furyl group, 2-furyl group, 3-thienyl group, 2-thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-
Benzoxazolyl group, 2-benzothiazolyl group, 2-
Benzimidazolyl group, 4-methylphenyl group, 3-methylphenyl group, 2-methylphenyl group, 4-ethylphenyl group, 3-ethylphenyl group, 2-ethylphenyl group, 4-n-propylphenyl group, 4-isopropyl Phenyl group, 2-isopropylphenyl group, 4-n-butylphenyl group, 4-isobutylphenyl group, 4-sec −
Butylphenyl group, 2-sec-butylphenyl group, 4-
tert-butylphenyl group, 3-tert-butylphenyl group, 2-tert-butylphenyl group, 4-n-pentylphenyl group, 4-isopentylphenyl group, 2-neopentylphenyl group, 4-tert-pentylphenyl Group, 4-
n-hexylphenyl group, 4- (2′-ethylbutyl)
Phenyl group, 4-n-heptylphenyl group, 4-n-octylphenyl group, 4- (2'-ethylhexyl) phenyl group, 4-tert-octylphenyl group, 4-n-decylphenyl group, 4-cyclopentylphenyl Group, 4-cyclohexylphenyl group, 4- (4'-methylcyclohexyl) phenyl group, 4- (4'-tert-butylcyclohexyl) phenyl group, 3-cyclohexylphenyl group, 2-cyclohexylphenyl group, 4-ethyl- 1-
Naphthyl group, 6-n-butyl-2-naphthyl group, 2,4
-Dimethylphenyl group, 2,5-dimethylphenyl group,
3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,6-dimethylphenyl group, 2,4-diethylphenyl group, 2,3,5-trimethylphenyl group,
3,6-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,6-diethylphenyl group, 2,5-
Diisopropylphenyl group, 2,6-diisobutylphenyl group, 2,4-di-tert-butylphenyl group, 2,5
-Di-tert-butylphenyl group, 4,6-di-tert-butyl-2-methylphenyl group, 5-tert-butyl-2-
Methylphenyl group, 4-tert-butyl-2,6-dimethylphenyl group,

4-methoxyphenyl, 3-methoxyphenyl, 2-methoxyphenyl, 4-ethoxyphenyl, 3-ethoxyphenyl, 2-ethoxyphenyl, 4-n-propoxyphenyl, 3-n -Propoxyphenyl group, 4-isopropoxyphenyl group, 2-
Isopropoxyphenyl group, 4-n-butoxyphenyl group, 4-isobutoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-
Isopentyloxyphenyl group, 2-isopentyloxyphenyl group, 4-neopentyloxyphenyl group, 2
-Neopentyloxyphenyl group, 4-n-hexyloxyphenyl group, 2- (2'-ethylbutyl) oxyphenyl group, 4-n-octyloxyphenyl group, 4-n
-Decyloxyphenyl group, 4-cyclohexyloxyphenyl group, 2-cyclohexyloxyphenyl group, 2
-Methoxy-1-naphthyl group, 4-methoxy-1-naphthyl group, 4-n-butoxy-1-naphthyl group, 5-ethoxy-1-naphthyl group, 6-methoxy-2-naphthyl group, 6-ethoxy- 2-naphthyl group, 6-n-butoxy-2-naphthyl group, 6-n-hexyloxy-2-naphthyl group, 7-methoxy-2-naphthyl group, 7-n-butoxy-2-naphthyl group, 2- Methyl-4-methoxyphenyl group, 2-methyl-5-methoxyphenyl group, 3-methyl-5-methoxyphenyl group, 3-ethyl-5-methoxyphenyl group, 2-methoxy-4-methylphenyl group, 3- A methoxy-4-methylphenyl group, a 2,4-dimethoxyphenyl group, a 2,5-dimethoxyphenyl group,
2,6-dimethoxyphenyl group, 3,4-dimethoxyphenyl group, 3,5-dimethoxyphenyl group, 3,5-diethoxyphenyl group, 3,5-di-n-butoxyphenyl group, 2-methoxy-4 -Ethoxyphenyl group, 2-methoxy-6-ethoxyphenyl group, 3,4,5-trimethoxyphenyl group, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 4- (4 ′
-Methylphenyl) phenyl group, 4- (3'-methylphenyl) phenyl group, 4- (4'-methoxyphenyl)
A phenyl group, a 4- (4′-n-butoxyphenyl) phenyl group, a 2- (2′-methoxyphenyl) phenyl group,
4- (4′-chlorophenyl) phenyl group, 3-methyl-4-phenylphenyl group, 3-methoxy-4-phenylphenyl group,

4-fluorophenyl, 3-fluorophenyl, 2-fluorophenyl, 4-chlorophenyl, 3-chlorophenyl, 2-chlorophenyl,
4-bromophenyl group, 2-bromophenyl group, 4-chloro-1-naphthyl group, 4-chloro-2-naphthyl group,
6-bromo-2-naphthyl group, 2,3-difluorophenyl group, 2,4-difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group,
3,4-difluorophenyl group, 3,5-difluorophenyl group, 2,3-dichlorophenyl group, 2,4-dichlorophenyl group, 2,5-dichlorophenyl group, 3,4
-Dichlorophenyl group, 3,5-dichlorophenyl group,
2,5-dibromophenyl group, 2,4,6-trichlorophenyl group, 2,4-dichloro-1-naphthyl group,
6-dichloro-2-naphthyl group, 2-fluoro-4-methylphenyl group, 2-fluoro-5-methylphenyl group, 3-fluoro-2-methylphenyl group, 3-fluoro-4-methylphenyl group, 2 -Methyl-4-fluorophenyl group, 2-methyl-5-fluorophenyl group, 3
-Methyl-4-fluorophenyl group, 2-chloro-4-
Methylphenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-
3-chlorophenyl group, 2-methyl-4-chlorophenyl group, 3-methyl-4-chlorophenyl group, 2-chloro-4,6-dimethylphenyl group, 2-methoxy-4-fluorophenyl group, 2-fluoro-4 -Methoxyphenyl group, 2-fluoro-4-ethoxyphenyl group, 2-fluoro-6-methoxyphenyl group, 3-fluoro-4-
Examples thereof include an ethoxyphenyl group, a 3-chloro-4-methoxyphenyl group, a 2-methoxy-5-chlorophenyl group, a 3-methoxy-6-chlorophenyl group, and a 5-chloro-2,4-dimethoxyphenyl group. However, the present invention is not limited to these.

At least one of Ar _{1 to} Ar ₄ represents a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, or a substituted or unsubstituted biphenyl group. Or an unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, or a substituted or unsubstituted biphenyl group, more preferably an unsubstituted or halogen atom, having 1 to 6 carbon atoms.
Or a total of 10 to 10 carbon atoms which may be mono- or polysubstituted by an alkyl group or an alkoxy group having 1 to 6 carbon atoms.
A naphthyl group of 20; an anthryl group having a total of 14 to 20 carbon atoms; or a biphenyl group having a total of 12 to 20 carbon atoms, particularly preferably an unsubstituted or an alkyl group having 1 to 6 carbon atoms, or a 1 to 1 carbon atom. A naphthyl group having 10 to 20 carbon atoms, an anthryl group having 14 to 20 carbon atoms, or a biphenyl group having 12 to 20 carbon atoms, which may be mono- or polysubstituted with 6 alkoxy groups.

In the compound represented by the general formula (1),
R ₁ and R ₂ are a linear, branched or cyclic alkyl group,
Alternatively, it represents a substituted or unsubstituted aralkyl group, preferably a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group). , Isobutyl group, se
c-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, 3,3-dimethylbutyl group, cyclohexyl group, n-heptyl group, Cyclohexylmethyl group, n-octyl group, tert-octyl group, 2
-Ethylhexyl group, n-nonyl group, n-decyl group, n
-Dodecyl group, n-tetradecyl group, n-hexadecyl group and the like, and substituted or unsubstituted aralkyl groups having 7 to 16 carbon atoms (for example, benzyl group, phenethyl group, α-methylbenzyl group, α, α-dimethylbenzyl) Group, 1-naphthylmethyl group, 2-naphthylmethyl group, furfuryl group,
2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 4-ethylbenzyl group, 4-isopropylbenzyl group, 4-tert-butylbenzyl group, 4-n
-Hexylbenzyl group, 3,4-dimethylbenzyl group,
3-methoxybenzyl group, 4-methoxybenzyl group, 4
-Ethoxybenzyl group, 4-n-butoxybenzyl group,
4-fluorobenzyl group, 3-fluorobenzyl group, 2
-Chlorobenzyl group, 4-chlorobenzyl group, etc.), more preferably, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aralkyl group having 7 to 10 carbon atoms. .

Specific examples of the compound represented by the general formula (1) according to the present invention include, for example, the following compounds, but the present invention is not limited thereto. -Exemplified compound number (Group A) A-1. 9,9-dimethyl-2,7-bis [N- (1′-naphthyl) -N-phenylamino] fluorene 9,9-dimethyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -methylphenyl) amino] fluorene 3.9,9-dimethyl-2,7-bis [N- ( 1'-naphthyl) -N- (3 "-methylphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (1′-naphthyl) -N- (2 ″ -methylphenyl) amino] fluorene 5.9,9-dimethyl-2,7-bis [N- ( 1'-naphthyl) -N- (4 "-ethylphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -tert-butylphenyl) amino] fluorene 7.9,9-dimethyl-2,7-bis [N -(1'-naphthyl) -N- (4 "-cyclohexylphenyl) amino] fluorene8. 8. 9,9-dimethyl-2,7-bis [N- (1'-naphthyl) -N- (2 ", 4" -dimethylphenyl) amino] fluorene 9. 9,9-dimethyl-2,7-bis [N- (1′-naphthyl) -N- (3 ″, 4 ″ -dimethylphenyl) amino] fluorene 9.9,9-Dimethyl-2,7-bis [N- (4′-methyl-1′-naphthyl) -N- (3 ″, 5 ″ -dimethylphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -methoxyphenyl) amino] fluorene 12.9,9-dimethyl-2,7-bis [N- ( 1'-naphthyl) -N- (3 "-methoxyphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -ethoxyphenyl) amino] fluorene 14.9,9-dimethyl-2,7-bis [N- ( 1'-naphthyl) -N- (3 "-fluorophenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (1′-naphthyl) -N- (3 ″ -chlorophenyl) amino] fluorene 16.9,9-dimethyl-2,7-bis [N- (4 '-Ethyl-1'-naphthyl) -N-phenylamino] fluorene 17.9,9-dimethyl-2,7-bis [N- (4'-methoxy-1'-naphthyl) -N-phenylamino Fluorene 18.9,9-diethyl-2,7-bis [N- (1'-naphthyl) -N-phenylamino] fluorene 19.9,9-diethyl-2,7-bis [N- (1 ' -Naphthyl) -N- (4 "-methylphenyl) amino] fluorene 20. 9,9-diethyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -methoxyphenyl) amino] fluorene 21.9,9-di-n-propyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -ethoxyphenyl) amino] fluorene 9,9-diisopropyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -methylphenyl) amino] fluorene

[0015] 23. 9,9-di-n-butyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -chlorophenyl) amino] fluorene 24.9,9-diisobutyl-2,7-bis [ N- (1′-naphthyl) -N- (4 ″ -methylphenyl) amino] fluorene 25. 9,9-di-n-pentyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -ethylphenyl) amino] fluorene 26. 9,9-di-n-hexyl-2 27., 7-Bis [N- (1'-naphthyl) -N- (4 "-phenylphenyl) amino] fluorene 27. 9,9-di-n-octyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -methoxyphenyl) amino] fluorene 28.9,9-di-n-decyl-2 , 7-bis [N- (1'-naphthyl) -N-phenylamino] fluorene 29.9,9-di-n-tetradecyl-2,7-bis [N- (1'-naphthyl) -N- (4 "-ethoxyphenyl) amino] fluorene 30. 9-Methyl-9-ethyl-2,7-bis [N- (1'-naphthyl) -N-phenylamino] fluorene 9-methyl-9-isopropyl-2,7-bis [N- (1′-naphthyl) -N- (4 ″ -methylphenyl) amino] fluorene 32.9-methyl-9-n-butyl-2, 7-bis [N- (4'-methoxy-1'-naphthyl) -N-phenylamino] fluorene 33.9-ethyl-9-n-hexyl-2,7-bis [N- (1'-naphthyl) ) -N- (4 "-ethoxyphenyl) amino] fluorene; 9,9-dimethyl-2- [N- (1'-naphthyl) -N-phenylamino] -7- [N, N-bis (4 "-methylphenyl) amino] fluorene 35.9,9-dimethyl -2- [N- (1'-naphthyl) -N- (4 "-methylphenyl) amino] -7- [N, N-bis (4" '-methylphenyl) amino] fluorene 36.9,9- 37. Diethyl-2- [N- (1'-naphthyl) -N- (4 "-methylphenyl) amino] -7- (N, N-diphenylamino) fluorene 9,9-dibenzyl-2,7-bis [N- (1'-naphthyl) -N-phenylamino] fluorene 9,9-diphenethyl-2,7-bis [N- (1'-naphthyl) -N-phenylamino] fluorene 9,9-di (4'-methylbenzyl) -2,7-bis [N- (1'-naphthyl) -N-phenylamino] fluorene 9,9-di (4'-methoxybenzyl) -2,7-bis [N- (1'-naphthyl) -N-phenylamino] fluorene 9.9,9-di (4'-chlorobenzyl) -2,7-bis [N- (1'-naphthyl) -N-phenylamino] fluorene 9,9-dibenzyl-2- [N- (1'-naphthyl) -N-phenylamino] -7- [N, N-di (4 "-methylphenyl) amino] fluorene 43.9-methyl-9 -(4'-methylbenzyl) -2,7-bis [N- (1 "-naphthyl) -N-phenylamino] fluorene 44. 9-ethyl-9-benzyl-2,7-bis [N- (1 "-naphthyl) -N-phenylamino] fluorene

[0016] 45. 9,9-dimethyl-2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene; 9,9-dimethyl-2,7-bis [N- (2′-naphthyl) -N- (4 ″ -methylphenyl) amino] fluorene 47.9,9-dimethyl-2,7-bis [N- ( 2'-naphthyl) -N- (3 "-methylphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (6'-methoxy-2'-naphthyl) -N-phenylamino] fluorene 9,9-dimethyl-2,7-bis [N- (6'-n-butoxy-2'-naphthyl) -N- (4 "-methylphenyl) amino] fluorene 50. 9,9-diethyl-2, 7-bis [N- (2'-naphthyl) -N- (3 "-methylphenyl) amino] fluorene 52. 9,9-di-n-propyl-2,7-bis [N- (2'-naphthyl) -N- (3 ", 4" -dimethylphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (2′-naphthyl) -N- (4 ″ -methoxyphenyl) amino] fluorene 53.9 9,9-diethyl-2,7-bis [N- ( 2'-naphthyl) -N- (3 "-ethoxyphenyl) amino] fluorene 9,9-di-n-butyl-2,7-bis [N- (2′-naphthyl) -N- (4 ″ -phenylphenyl) amino] fluorene 55.9-methyl-9-ethyl-2,7 -Bis [N- (2'-naphthyl) -N- (4 "-methylphenyl) amino] fluorene 56. 9-ethyl-9-n-butyl-2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene 9,9-dimethyl-2- [N- (2'-naphthyl) -N-phenylamino] -7- [N, N-bis (4 "-methylphenyl) amino] fluorene 58.9,9-dimethyl -2- [N- (2'-naphthyl) -N- (4 "-methylphenyl) amino] -7- [N, N-bis (4" '-methylphenyl) amino] fluorene 59.9,9- 60. Diethyl-2- [N- (2'-naphthyl) -N- (4 "-methylphenyl) amino] -7- (N, N-diphenylamino) fluorene 9,9-dibenzyl-2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene 9,9-diphenethyl-2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene 9,9-di (4'-methylbenzyl) -2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene63. 9,9-di (4'-methoxybenzyl) -2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene 9,9-di (4'-chlorobenzyl) -2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene 66. 9-methyl-9- (4'-chlorobenzyl) -2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene 9-ethyl-9-benzyl-2,7-bis [N- (2'-naphthyl) -N-phenylamino] fluorene

(Group B) B-1. 9,9-dimethyl-2,7-bis [N- (2'-anthryl) -N-phenylamino] fluorene 9,9-dimethyl-2,7-bis [N- (2′-anthryl) -N- (4 ″ -methylphenyl) amino] fluorene 3.9,9-dimethyl-2,7-bis [N- ( 2'-anthryl) -N- (3 "-methylphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (2′-anthryl) -N- (4 ″ -methoxyphenyl) amino] fluorene 5.9,9-dimethyl-2,7-bis [N- ( 2'-anthryl) -N- (3 "-ethoxyphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (2′-anthryl) -N- (3 ″ -fluorophenyl) amino] fluorene 7.9,9-diethyl-2,7-bis [N- ( 2'-anthryl) -N-phenylamino] fluorene 8.9,9,9-di-n-propyl-2,7-bis [N- (2'-anthryl) -N- (4 "-methylphenyl) amino] Fluorene 9. 9. 9,9-di-n-butyl-2,7-bis [N- (2'-anthryl) -N-phenylamino] fluorene 9,9-di-n-hexyl-2,7-bis [N- (2′-anthryl) -N- (4 ″ -methylphenyl) amino] fluorene 11.9-methyl-9-ethyl-2,7 -Bis [N- (2'-anthryl) -N-phenylamino] fluorene 12.9,9-dimethyl-2- [N- (2'-anthryl) -N-phenylamino] -7- (N, N -Diphenylamino) fluorene 13.9,9-Diethyl-2- [N- (2'-anthryl) -N-phenylamino] -7- [N, N-di (4 "'-methylphenyl) amino] fur Oren 14. 9.9,9-dibenzyl-2,7-bis [N- (2'-anthryl) -N-phenylamino] fluorene 9,9-di (4'-methylbenzyl) -2,7-bis [N- (2 "-anthryl) -N-phenylamino] fluorene 16.9-ethyl-9-benzyl-2,7-bis [ N- (2'-anthryl) -N-phenylamino] fluorene 17.9,9-dimethyl-2,7-bis [N- (9'-anthryl) -N-phenylamino] fluorene 18.9,9- 18. Dimethyl-2,7-bis [N- (9'-anthryl) -N- (3 "-methylphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (9′-anthryl) -N- (4 ″ -ethylphenyl) amino] fluorene 20.9,9-dimethyl-2,7-bis [N- ( 9'-anthryl) -N- (4 "-methoxyphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (9′-anthryl) -N- (3 ″ -fluorophenyl) amino] fluorene 22.9,9-Diethyl-2,7-bis [N- ( 9'-anthryl) -N-phenylamino] fluorene 23. 9,9-di-n-propyl-2,7-bis [N- (9'-anthryl) -N- (4 "-methylphenyl) amino] Fluorene 24. 9,9-di-n-butyl-2,7-bis [N- (9'-anthryl) -N-phenylamino] fluorene; 26. 9-methyl-9-ethyl-2,7-bis [N- (9'-anthryl) -N-phenylamino] fluorene 9.9,9-dimethyl-2- [N- (9'-anthryl) -N-phenylamino] -7- (N, N-diphenylamino) fluorene 9,9-Diethyl-2- [N- (9'-anthryl) -N-phenylamino] -7- [N, N-di (4 "-methylphenyl) amino] fluorene 28.9,9-dibenzyl -2,7-bis [N- (9'-anthryl) -N-phenylamino] fluorene 29.9-ethyl-9-benzyl-2,7-bis [N- (9'-anthryl) -N-phenyl Amino] fluorene

(Group C) C-1. 9,9-dimethyl-2,7-bis [N- (4'-phenylphenyl) -N-phenylamino] fluorene 9,9-dimethyl-2,7-bis [N- (4'-phenylphenyl) -N- (4 "-methylphenyl) amino] fluorene 3.9,9-dimethyl-2,7-bis [N- (4′-phenylphenyl) -N- (3 ″ -methylphenyl) amino] fluorene 9,9-dimethyl-2,7-bis [N- (4′-phenylphenyl) -N- (4 ″ -ethylphenyl) amino] fluorene 5.9,9-dimethyl-2,7-bis [N- 5. [4 '-(4 "-methylphenyl) phenyl] -N-phenylamino] fluorene 9,9-Dimethyl-2,7-bis [N- [4 '-(4 "-methoxyphenyl) phenyl] -N-phenylamino] fluorene 7.9,9-Diethyl-2,7-bis [N- (4'-phenylphenyl) -N-phenylamino] fluorene 8.9,9-di-n-propyl-2,7-bis [N- (4'-phenylphenyl) -N- (3 "-methylphenyl 8.) Amino] fluorene 9,9-di-n-butyl-2,7-bis [N- (4'-phenylphenyl) -N-phenylamino] fluorene 9,9-di-n-pentyl-2,7-bis [N- (4'-phenylphenyl) -N- (4 "-methylphenyl) amino] fluorene 11.9,9-di-n-hexyl- 12.7-bis [N- (4′-phenylphenyl) -N- (4 ″ -methoxyphenyl) amino] fluorene 9,9-di-n-octyl-2,7-bis [N- (4 '-[4 "-methylphenyl] phenyl) -N-phenylamino] fluorene 13.9,9-di- (2'- 13. Ethylhexyl) -2,7-bis [N- (4 '-[4 "-methoxyphenyl] phenyl) -N-phenylamino] fluorene 9. 9-methyl-9-ethyl-2,7-bis [N- (4'-phenylphenyl) -N-phenylamino] fluorene 9-ethyl-9-n-propyl-2,7-bis [N- (4'-phenylphenyl) -N- (4 "-methylphenyl) amino] fluorene 16.9,9-dimethyl-2- [N -(4'-phenylphenyl) -N-phenylamino] -7- (N, N-diphenylamino) fluorene 17.9,9-dimethyl-2- [N- (4'-phenylphenyl) -N- ( 4 "-methylphenyl) amino] -7- (N, N-diphenylamino) fluorene 9,9-Diethyl-2- [N- (4'-phenylphenyl) -N- (4 "-methylphenyl) amino] -7- [N, N-di (4" '-methylphenyl) amino] fluorene 19. 9. 9,9-dibenzyl-2,7-bis [N- (4'-phenylphenyl) -N-phenylamino] fluorene 9,9-dibenzyl-2- [N- (4'-phenylphenyl) -N- (4 "-methylphenyl) amino] -7- [N, N-di (4" '-methylphenyl) amino] fluorene 21. 9-methyl-9-benzyl-2,7-bis [N- (4'-phenylphenyl) -N-phenylamino] fluorene

The compound represented by the general formula (1) can be produced by a method known per se. That is, for example, it can be produced by reacting a compound represented by the general formula (2-A) (Formula 4) with an aryl halide derivative in the presence of a copper compound (Ullman reaction). Further, for example, it can also be produced by reacting a compound represented by the general formula (2-B) (Formula 4) with an N, N-diarylamine derivative in the presence of a copper compound (Ullman reaction).

[0020]

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The organic electroluminescent element usually has at least one light-emitting layer containing at least one light-emitting component sandwiched between a pair of electrodes. In consideration of the functional levels of hole injection and hole transport, electron injection and electron transport of the compound used in the light-emitting layer, a hole injection transport layer containing a hole injection transport component and / or An electron injection / transport layer containing an injection / transport component can also be provided. For example, when the compound used for the light emitting layer has a good hole injecting function, a hole transporting function or / and an electron injecting function, and an electron transporting function, the light emitting layer is preferably a hole injecting / transporting layer or / and an electron injecting / transporting layer. The element can also be configured to serve as Of course, depending on the case, a structure of a device (single-layer device) without both the hole injection transport layer and the electron injection transport layer may be employed. Further, each of the hole injection transport layer, the electron injection transport layer and the light emitting layer may have a single-layer structure or a multilayer structure,
The hole injecting and transporting layer and the electron injecting and transporting layer can be formed by separately providing a layer having an injection function and a layer having a transport function in each layer.

In the organic electroluminescent device of the present invention, the compound represented by the general formula (1) is preferably used for a hole injection / transport component and / or a light emitting component, and more preferably used for a hole injection / transport component. preferable. In the organic electroluminescent device of the present invention, the compound represented by the general formula (1) may be used alone or in combination.

The structure of the organic electroluminescent device of the present invention is not particularly limited.
Hole injection / transport layer / emission layer / electron injection / transport layer / cathode device (FIG. 1), (B) anode / hole injection / transport layer / emission layer / cathode device (FIG. 2), (C) anode / emission Layer / electron injection / transport layer / cathode type device (FIG. 3), (D) anode / light emitting layer / cathode type device (FIG. 4) and the like. Further, the device is of a type in which a light emitting layer is sandwiched between electron injection and transport layers (E).
Anode / hole injection / transport layer / electron injection / transport layer / emission layer / electron injection / transport layer / cathode type device (FIG. 5).
The element configuration of the (D) type is, of course, an element of a type in which a light emitting component is sandwiched between a pair of electrodes in a single layer form, and further, for example, (F) a hole injection / transport component, a light emitting component, An element of a type in which an electron injection / transport component is mixed and sandwiched between a pair of electrodes (FIG. 6), and (G) a layer in which a hole injection / transport component and a light emitting component are mixed, between a pair of electrodes. There is an element of the sandwiched type (FIG. 7) and an element of the type (H) sandwiched between a pair of electrodes in the form of a single layer in which a light emitting component and an electron injection / transport component are mixed (FIG. 8).

The organic electroluminescent device of the present invention is not limited to these device structures, and each type of device may be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. it can. In each type of device, a light emitting component is provided between the hole injecting and transporting layer and the light emitting layer, or a mixed layer of the hole injecting and transporting component and the light emitting component and / or between the light emitting layer and the electron injecting and transporting layer. And a mixed layer of an electron injection and transport component. More preferred configurations of the organic electroluminescent device are (A) type device, (B) type device, (E)
Type element, (F) type element or (G) type element, and more preferably (A) type element, (B) type element, (F) type element or (G) type element.

As the organic electroluminescent device of the present invention, for example, (A) anode / hole injection / transport layer / emission layer / electron injection / transport layer / cathode device shown in FIG. 1 will be described.
In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection / transport layer, 4 is a light emitting layer, 5 is an electron injection / transport layer, 6 is a cathode,
Reference numeral 7 denotes a power supply.

The organic electroluminescent device of the present invention is preferably supported on a substrate 1. The substrate is not particularly limited, but is preferably transparent or translucent. Transparent plastic sheet (for example, polyester, polycarbonate, polysulfone, polymethyl methacrylate, polypropylene,
A sheet made of polyethylene or the like), a translucent plastic sheet, quartz, a transparent ceramic, or a composite sheet combining these. Further, the luminescent color can be controlled by combining, for example, a color filter film, a color conversion film, and a dielectric reflection film on the substrate.

As the anode 2, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively large work function as an electrode material. As the electrode material used for the anode, for example, gold, platinum, silver, copper, cobalt, nickel,
Palladium, vanadium, tungsten, tin oxide, zinc oxide, ITO (indium tin oxide), polythiophene, polypyrrole, and the like can be given. These electrode substances may be used alone or in combination of two or more. The anode can be formed on the substrate by using such an electrode material by a method such as a vapor deposition method and a sputtering method. Further, the anode may have a single-layer structure or a multilayer structure. The sheet electric resistance of the anode is preferably several hundred Ω / □.
Hereinafter, more preferably, it is set to about 5 to 50 Ω / □. The thickness of the anode depends on the material of the electrode substance to be used, but is generally about 5 to 1000 nm, more preferably,
It is set to about 10 to 500 nm.

The hole injection / transport layer 3 is a layer containing a compound having a function of facilitating the injection of holes (holes) from the anode and a function of transporting the injected holes. The hole injecting and transporting layer includes a compound represented by the general formula (1) and / or another compound having a hole injecting and transporting function (for example, a phthalocyanine derivative, a triarylmethane derivative, a triarylamine derivative, an oxazole derivative,
Hydrazone derivative, stilbene derivative, pyrazoline derivative, polysilane derivative, polyphenylenevinylene and its derivative, polythiophene and its derivative, poly-
N-vinylcarbazole derivative). The compounds having a hole injection / transport function may be used alone or in combination. In the organic electroluminescent device of the present invention, the hole injecting and transporting layer preferably contains the compound represented by the general formula (1).

Other compounds having a hole injection / transport function used in the present invention include triarylamine derivatives (for example, 4,4′-bis [N-phenyl-N- (4 ″)).
-Methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] biphenyl, 4,4'-bis [N-phenyl-N-
(3 "-methoxyphenyl) amino] biphenyl, 4,
4'-bis [N-phenyl-N- (1 "-naphthyl) amino] biphenyl, 3,3'-dimethyl-4,4'-bis [N-phenyl-N- (3" -methylphenyl) amino] Biphenyl, 1,1-bis [4 ′-[N, N-di (4 ″ -methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N- (4′-methylphenyl) -N- (4 "-N-butylphenyl) amino] phenanthrene, 3,8-bis (N, N-diphenylamino) -6-phenylphenanthridine, 4-methyl-
N, N-bis [4 ", 4"'-bis[N',N'-di (4
-Methylphenyl) amino] biphenyl-4'-yl]
Aniline, N, N'-bis [4- (diphenylamino)
Phenyl] -N, N'-diphenyl-1,3-diaminobenzene, N, N'-bis [4- (diphenylamino)
Phenyl] -N, N'-diphenyl-1,4-diaminobenzene, 5,5 "-bis [4- (bis [4-methylphenyl] amino) phenyl] -2,2 ': 5', 2"-
Terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ′, 4 ″ -tris (N-carbazolyl) triphenylamine, 4,4 ′, 4 ″ -tris [N- (3 ″ ″ -Methylphenyl) -N-phenylamino] triphenylamine, 1,3,5-tris [4'-
Diphenylaminophenyl) phenylamino] benzene), polythiophene and its derivatives, poly-N-
Vinyl carbazole derivatives are more preferred. When the compound represented by the general formula (1) and another compound having a hole injecting and transporting function are used in combination, the proportion of the compound represented by the general formula (1) in the hole injecting and transporting layer is preferably ,
0.1% by weight or more, more preferably 0.1 to 99.9.
% By weight, more preferably about 1 to 99% by weight,
Particularly preferably, it is adjusted to about 5 to 95% by weight.

The light emitting layer 4 has a function of injecting holes and electrons,
This is a layer containing a compound having a transport function thereof and a function of generating excitons by recombination of holes and electrons. The light-emitting layer includes a compound represented by the general formula (1) and / or a compound having another light-emitting function (eg, an acridone derivative, a quinacridone derivative, a polycyclic aromatic compound [eg,
Rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-
Bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, 4,4 ′
-Bis (9 "-ethynylanthracenyl) biphenyl], a triarylamine derivative (for example, the compounds described above as compounds having a hole injecting and transporting function), and an organometallic complex [for example, tris (8- Quinolinolate) aluminum, bis (10-benzo [h]
Quinolinolate) beryllium, zinc salt of 2- (2'-hydroxyphenyl) benzoxazole, 2- (2'-
4-hydroxyphenyl) benzothiazole zinc salt, 4-
Zinc salts of hydroxyacridine], stilbene derivatives [eg, 1,1,4,4-tetraphenyl-1,3-
Butadiene, 4,4'-bis (2,2-diphenylvinyl) biphenyl], coumarin derivative [for example, coumarin 1, coumarin 6, coumarin 7, coumarin 30, coumarin 106, coumarin 138, coumarin 151, coumarin 1
52, coumarin 153, coumarin 307, coumarin 31
1. Coumarin 314, Coumarin 334, Coumarin 33
8, coumarin 343, coumarin 500], pyran derivatives [for example, DCM1, DCM2], oxazone derivatives [for example, Nile Red], benzothiazole derivatives,
Benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamate derivatives, poly-
N-vinyl carbazole and its derivatives, polythiophene and its derivatives, polyphenylene and its derivatives, polyfluorene and its derivatives, polyphenylene vinylene and its derivatives, polybiphenylene vinylene and its derivatives, polyterphenylene vinylene and its derivatives, polynaphthylene vinylene and And at least one of its derivatives, polythienylenevinylene and derivatives thereof).

In the organic electroluminescent device of the present invention, the light emitting layer preferably contains the compound represented by the general formula (1). When the compound represented by the general formula (1) and the compound having another light emitting function are used in combination, the ratio of the compound represented by the general formula (1) in the light emitting layer is preferably 0.001 to 99. It is adjusted to about .999% by weight.

As the other compound having a light-emitting function used in the present invention, a polycyclic aromatic compound and a light-emitting organic metal complex are more preferable. For example, J. Appl. Phys., 65 , 36
10 (1989) and JP-A-5-214332, the light-emitting layer can be composed of a host compound and a guest compound (dopant). The compound represented by the general formula (1) can form a light-emitting layer as a host compound, and can also form a light-emitting layer as a guest compound. When the compound represented by the general formula (1) is used as a host compound to form a light-emitting layer, examples of the guest compound include the above compounds having other light-emitting functions, and among them, a polycyclic aromatic compound Is preferred. In this case, a compound having another light emitting function is added to the compound represented by the general formula (1) in an amount of 0.001 to 40.
% By weight, preferably, more preferably, 0.1 to 2%.
Use about 0% by weight. Examples of the polycyclic aromatic compound used in combination with the compound represented by the general formula (1) include, but are not limited to, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene,
Coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, 4,4 ′ -Bis (9 "-ethynylanthracenyl) biphenyl, etc. Of course, the polycyclic aromatic compound may be used alone or in combination.

When the compound represented by the general formula (1) is used as a guest compound to form a light-emitting layer, the host compound is preferably a light-emitting organometallic complex. In this case, the compound represented by the general formula (1) is preferably used in an amount of about 0.001 to 40% by weight, more preferably about 0.1 to 20% by weight, based on the luminescent organic metal complex. . The luminescent organometallic complex used in combination with the compound represented by the general formula (1) is not particularly limited, but a luminescent organoaluminum complex is preferable and has a substituted or unsubstituted 8-quinolinolate ligand. Luminescent organoaluminum complexes are more preferred. Preferred luminescent organic metal complexes include, for example, luminescent organic aluminum complexes represented by general formulas (a) to (c). (Q) ₃ -Al (a) (wherein Q represents a substituted or unsubstituted 8-quinolinolate ligand) (Q) ₂ -Al-OL (b) (where Q represents substituted 8 -Represents a quinolinolate ligand, O
-L is a phenolate ligand, and L represents a hydrocarbon group having 6 to 24 carbon atoms including a phenyl moiety.) (Q) ₂ -Al-O-Al- (Q) ₂ (c) Q represents a substituted 8-quinolinolate ligand)

Specific examples of the luminescent organometallic complex include, for example, tris (8-quinolinolate) aluminum, tris (4-methyl-8-quinolinolate) aluminum, tris (5-methyl-8-quinolinolate) aluminum, tris ( 3,4-dimethyl-8-quinolinolate) aluminum, tris (4,5-dimethyl-8-quinolinolate) aluminum, tris (4,6-dimethyl-8-quinolinolate) aluminum, bis (2-methyl-8-quinolinolate) (Phenolate) aluminum, bis (2-methyl-8-quinolinolate) (2-
Methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(4-methylphenolate) aluminum, bis (2-
Methyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum,
Bis (2-methyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2-methyl-8
-Quinolinolate) (2,3-dimethylphenolate)
Aluminum, bis (2-methyl-8-quinolinolate) (2,6-dimethylphenolate) aluminum,
Bis (2-methyl-8-quinolinolate) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3,5-dimethylphenolate) aluminum, bis (2-methyl-8- Quinolinolate) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolate)
(2,6-diphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2,4,6-
Triphenylphenolate) aluminum, bis (2-
Methyl-8-quinolinolate) (2,4,6-trimethylphenolate) aluminum, bis (2-methyl-8
-Quinolinolate) (2,4,5,6-tetramethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-methyl-8-quinolinolate) (2-naphtholate) ) Aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate)
(3-phenylphenolato) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-dimethylphenolate) ) Aluminum, bis (2,4-dimethyl-8-)
Quinolinolate) (3,5-di-tert-butylphenolato) aluminum, bis (2-methyl-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-8-quinolinolate) aluminum, bis (2,4 −
Dimethyl-8-quinolinolate) aluminum-μ-oxo-bis (2,4-dimethyl-8-quinolinolate)
Aluminum, bis (2-methyl-4-ethyl-8-quinolinolate) aluminum-μ-oxo-bis (2-
Methyl-4-ethyl-8-quinolinolate) aluminum, bis (2-methyl-4-methoxy-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-
4-methoxy-8-quinolinolate) aluminum, bis (2-methyl-5-cyano-8-quinolinolate) aluminum-μ-oxo-bis (2-methyl-5-cyano-8-quinolinolate) aluminum, bis (2- Methyl-5-trifluoromethyl-8-quinolinolate)
Aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolate) aluminum and the like can be mentioned. Of course, the luminescent organometallic complex may be used alone or in combination.

The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating the injection of electrons from the cathode and a function of transporting the injected electrons. Examples of the compound having an electron injecting and transporting function used in the electron injecting and transporting layer include, for example, organometallic complexes [eg, tris (8-quinolinolate) aluminum, bis (10-benzo [h] quinolinolate) beryllium], oxadiazole Derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorenone derivatives, thiopyrandioxide derivatives and the like can be mentioned. The compounds having an electron injection / transport function may be used alone or in combination.

As the cathode 6, it is preferable to use a metal, an alloy or an electrically conductive compound having a relatively small work function as an electrode material. Examples of the electrode material used for the cathode include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium,
Manganese, yttrium, aluminum, an aluminum-lithium alloy, an aluminum-calcium alloy, an aluminum-magnesium alloy, a graphite thin film, and the like can be given. These electrode substances may be used alone or in combination of two or more. The cathode, these electrode substances, for example, a vapor deposition method, a sputtering method,
It can be formed on the electron injection transport layer by a method such as an ionization vapor deposition method, an ion plating method, and a cluster ion beam method. Further, the cathode may have a single-layer structure or a multilayer structure. The sheet electric resistance of the cathode is preferably set to several hundreds Ω / □ or less. The thickness of the cathode depends on the material of the electrode substance used, but is generally about 5 to 1000 nm, more preferably,
It is set to about 10 to 500 nm. In order to efficiently extract the light emitted from the organic electroluminescent device, it is preferable that at least one of the anode and the cathode is transparent or translucent, and the transmittance of the emitted light is generally 70% or more. It is more preferable to set the material and thickness of the anode.

In the organic electroluminescent device of the present invention, at least one layer may contain a singlet oxygen quencher. The singlet oxygen quencher is not particularly limited and includes, for example, rubrene,
Nickel complexes, diphenylisobenzofuran and the like can be mentioned, and rubrene is particularly preferred. The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injection transport layer, and more preferably a hole injection transport layer.
For example, when a singlet oxygen quencher is contained in the hole injecting and transporting layer, the singlet oxygen quencher may be contained uniformly in the hole injecting and transporting layer. (An electron injection / transport layer having a light emitting function). The content of the singlet oxygen quencher is from 0.01 to 50% by weight, preferably from 0.0 to 50% by weight of the total amount constituting the contained layer (for example, the hole injection / transport layer).
5 to 30% by weight, more preferably 0.1 to 20% by weight
It is.

The method for forming the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited. For example, a vacuum evaporation method, an ionization evaporation method, a solution coating method (for example, a spin coating method, a casting method, Method, dip coating method,
It can be manufactured by forming a thin film by a bar coating method, a roll coating method, a Langmuir-Brosette method, or the like. When forming each layer by a vacuum deposition method, the conditions of the vacuum deposition are not particularly limited,
It is carried out under a vacuum of about 10 ^-5 Torr or less, a boat temperature of about 50 to 400 ° C. (evaporation source temperature), a substrate temperature of about −50 to 300 ° C., and a deposition rate of about 0.005 to 50 nm / sec. Is preferred. In this case, by forming each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer continuously under a vacuum, an organic electroluminescent element having more excellent characteristics can be manufactured. When each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer is formed using a plurality of compounds by a vacuum deposition method, each boat containing the compounds is individually temperature-controlled and co-deposited. Is preferred.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin or the like are dissolved or dispersed in a solvent to form a coating liquid. Examples of the binder resin that can be used for each of the hole injection transport layer, the light emitting layer, and the electron injection transport layer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate, and the like.
Polymethyl methacrylate, polyether, polycarbonate, polyamide, polyimide, polyamide imide,
High molecular compounds such as polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and its derivatives, polythiophene and its derivatives, polyphenylenevinylene and its derivatives, polyfluorene and its derivatives, and polythienylenevinylene and its derivatives. . The binder resin may be used alone or in combination.

When each layer is formed by a solution coating method,
The components forming each layer or the components and a binder resin are combined with a suitable organic solvent (for example, hexane, octane,
Decane, toluene, xylene, ethylbenzene, hydrocarbon solvents such as 1-methylnaphthalene, for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as cyclohexanone, for example, dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, Halogenated hydrocarbon solvents such as tetrachloroethane, chlorobenzene, dichlorobenzene, and chlorotoluene, for example, ester solvents such as ethyl acetate, butyl acetate, and amyl acetate, for example, methanol, propanol, butanol, pentanol, hexanol, and cyclohexanol , Methyl cellosolve, ethyl cellosolve, alcohol solvents such as ethylene glycol, for example, dibutyl ether, tetrahydrofuran,
Dioxane, ether solvents such as anisole, for example,
Polar solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide) and / or dissolved in water Alternatively, a thin film can be formed by various coating methods by dispersing the mixture into a coating liquid.

The method of dispersion is not particularly limited. For example, the particles can be dispersed into fine particles using a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer or the like. The concentration of the coating solution is not particularly limited, and can be set to a concentration range suitable for producing a desired thickness by a coating method to be performed. Preferably, the solution concentration is about 1 to 30% by weight. When a binder resin is used, the amount of the binder resin used is not particularly limited. 5) to 99.9% by weight
Level, preferably about 10 to 99% by weight, more preferably about 15 to 90% by weight.

The thicknesses of the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer are not particularly limited, but are generally preferably set to about 5 nm to 5 μm.
A protective layer (sealing layer) may be provided on the fabricated device for the purpose of preventing contact with oxygen, moisture, or the like, or the device may be formed of, for example, paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite, It can be protected by being enclosed in an inert substance such as a contained fluorocarbon oil. Examples of the material used for the protective layer include organic polymer materials (for example, fluorinated resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene) , Polyphenylene oxide), inorganic materials (for example, diamond thin film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide,
Metal sulfide), and a photocurable resin. The material used for the protective layer may be used alone or in combination of two or more. The protective layer may have a single-layer structure or a multilayer structure.

Further, a metal oxide film (for example, an aluminum oxide film) or a metal fluoride film can be provided as a protective film on the electrode. Also, for example, on the surface of the anode,
For example, an interface layer (intermediate layer) composed of an organic phosphorus compound, polysilane, an aromatic amine derivative, and a phthalocyanine derivative
Can also be provided. Further, electrodes, eg, anodes, can be used by treating the surface with, eg, acid, ammonia / hydrogen peroxide, or plasma.

The organic electroluminescent device of the present invention is generally used as a DC-driven device, but can also be used as a pulse-driven or AC-driven device.
Incidentally, the applied voltage is generally about 2 to 30 V. The organic electroluminescent device of the present invention can be used for, for example, a panel light source, various light emitting devices, various display devices, various labels, various sensors, and the like.

[0045]

The present invention will be described in more detail with reference to the following examples, which, of course, are not intended to limit the scope of the present invention. Example 1 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 9,9-dimethyl-2,7-
Bis [N- (1′-naphthyl) -N-phenylaminophenyl] fluorene (compound of Exemplified Compound No. A-1)
Was deposited at a deposition rate of 0.2 nm / sec to a thickness of 75 nm to form a hole injecting and transporting layer. Then tris (8-quinolinolato) aluminum was deposited thereon with a deposition rate of 0,1.
Vapor deposition was performed at 2 nm / sec to a thickness of 50 nm to form a light emitting layer also serving as an electron injection transport layer. Further thereon, magnesium and silver were used as cathodes at a deposition rate of 0.2 nm / sec.
A cathode was formed by co-evaporation (weight ratio: 10: 1) to a thickness of 00 nm to produce an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. A direct current voltage is applied to the produced organic electroluminescent device, and at 50 ° C. in a dry atmosphere,
The device was continuously driven at a constant current density of 0 mA / cm ² . Initially, green light emission of 6.5 V and a luminance of 450 cd / m ² was confirmed. The half life of the luminance was 550 hours.

Examples 2 to 21 In Example 1, instead of using the compound of Exemplified Compound No. A-1 in forming the hole injecting and transporting layer, the compound of Exemplified Compound No. A-2 (Example 2) was used. Compound of Exemplified Compound No. A-9 (Example 3), Exemplified Compound No. A-2
Compound No. 0 (Example 4), Compound No. A-30 (Example 5), Compound No. A-35 (Example 6), Compound No. A-37 (Example 7) A compound of Exemplified Compound No. A-45 (Example 8), a compound of Exemplified Compound No. A-48 (Example 9),
Compound of Exemplified Compound No. A-54 (Example 10), Compound of Exemplified Compound No. A-57 (Example 11), Compound of Exemplified Compound No. B-1 (Example 12), Compound of Exemplified Compound No. B-7 (Example 13), Exemplified Compound No. B-1
Compound No. 2 (Example 14), Compound No. B-17 (Example 15), Compound No. B-21 (Example 16), Compound No. C-1 (Example 17) Compound of Exemplified Compound No. C-3 (Example 1)
8), Compound of Exemplified Compound No. C-17 (Example 1)
9), Compound of Exemplified Compound No. C-19 (Example 2)
0), Compound of Exemplified Compound No. C-21 (Example 21)
An organic electroluminescent device was produced by the method described in Example 1 except that was used. Green light emission was confirmed from each element. The characteristics were further examined, and the results are shown in Table 1 (Table 1).
It was shown to.

Comparative Examples 1-2 In Example 1, when forming the hole injecting and transporting layer, instead of using the compound of Exemplified Compound No. A-1, 4,
4'-bis [N-phenyl-N- (3 "-methylphenyl) amino] biphenyl (Comparative Example 1), 9,9-dimethyl-2,7-bis (N, N-diphenylamino) fluorene (Comparative Example) An organic electroluminescent device was prepared in the same manner as in Example 1 except that 2) was used, and green light emission was confirmed from each device, and the characteristics were further examined. )Pointing out toungue.

[0048]

[Table 1]

Example 22 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, poly (thiophene-2,5-
Diyl) was deposited at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection transport layer. Next, the compound of Exemplified Compound No. A-3 was deposited at a deposition rate of 0.2 nm / se.
Vacuum was deposited to a thickness of 55 nm at c to form a second hole injection / transport layer. Then, tris (8-quinolinolanote) aluminum was deposited thereon at a deposition rate of 0.2 nm / sec.
It was deposited to a thickness of nm to form a light emitting layer which also served as an electron injection transport layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. A DC voltage was applied to the produced organic electroluminescent device, and the device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, green light emission of 6.4 V and luminance of 450 cd / m ² was confirmed. The half life of the luminance was 1200 hours.

Example 23 A glass substrate having a 200 nm thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, 4,4 ′, 4 ″ -tris (N
-(3 "'-methylphenyl) -N-phenylamino] triphenylamine at a deposition rate of 0.1 nm / sec.
The first hole injection transport layer was deposited to a thickness of nm. Next, the compound of Exemplified Compound No. A-11 and rubrene were separated from different evaporation sources at a deposition rate of 0.2 nm / sec and a thickness of 20 nm.
Was co-evaporated to a thickness of 10: 1 (weight ratio: 10: 1) to obtain a light-emitting layer also serving as a second hole injection / transport layer. Subsequently, tris (8-quinolinolate) aluminum was deposited thereon at a deposition rate of 0.2.
The film was deposited at a thickness of 50 nm at a rate of nm / sec to form an electron injection transport layer. Further, magnesium and silver were co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode, thereby producing an organic electroluminescent device. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. A DC voltage was applied to the produced organic electroluminescent device, and the device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, yellow light emission of 6.2 V and a luminance of 470 cd / m ² was confirmed. The half life of the luminance was 1300 hours.

Example 24 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, poly (thiophene-2,5-
Diyl) was deposited at a deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection transport layer. After returning the vapor deposition tank to atmospheric pressure, the pressure of the vapor deposition tank was reduced again to 3 × 10 ⁻⁶ Torr. Next, the compound of Exemplified Compound No. B-2 and rubrene were separated from different evaporation sources at a deposition rate of 0.2 nm / sec.
A co-evaporation (weight ratio: 10: 1) was performed to a thickness of 5 nm to obtain a light emitting layer also serving as a second hole injection / transport layer. While maintaining the reduced pressure state, tris (8-quinolinolate) was further placed thereon.
Aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form an electron injecting and transporting layer. While maintaining the reduced pressure, magnesium and silver were further co-deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 200 nm (weight ratio: 10: 1) to form a cathode to produce an organic electroluminescent device. did. A DC voltage was applied to the produced organic electroluminescent device, and the device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, yellow light emission of 6.2 V and a luminance of 450 cd / m ² was confirmed. The half life of the luminance was 1500 hours.

Example 25 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, the compound of Exemplified Compound No. B-4 was vapor-deposited on the ITO transparent electrode at a vapor deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole injection transport layer. Next, the compound of Exemplified Compound No. A-1 and rubrene were separated from different evaporation sources,
Co-deposition (weight ratio: 10: 1) was performed at a deposition rate of 0.2 nm / sec to a thickness of 55 nm to obtain a light-emitting layer also serving as a second hole injection / transport layer. Further, tris (8-quinolinolate) aluminum was further deposited thereon at a deposition rate of 0.2 nm / sec.
Evaporation was performed to a thickness of 0 nm to form an electron injection transport layer. Further thereon, magnesium and silver were deposited at a deposition rate of 0.2 nm /
A co-evaporation (weight ratio: 10: 1) was performed to a thickness of 200 nm in sec to form an organic electroluminescent device as a cathode. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. Apply a DC voltage to the produced organic electroluminescent device, and in a dry atmosphere,
The device was continuously driven at a constant current density of 10 mA / cm ² . Initially, yellow light emission of 6.1 V and a luminance of 440 cd / m ² was confirmed. The half life of the luminance was 1600 hours.

Example 26 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas, further washed with UV / ozone, fixed to a substrate holder of a vapor deposition device, and then the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. First, a compound of Exemplified Compound No. A-10 was deposited on an ITO transparent electrode to a thickness of 55 nm at a deposition rate of 0.2 nm / sec to form a hole injection transport layer. Next, tris (8-quinolinolato) aluminum and a compound of Exemplified Compound No. C-2 were further deposited thereon at a deposition rate of 0.2 nm / sec.
A co-evaporation (weight ratio 10: 1) was performed to a thickness of 0 nm to form a light emitting layer. Further, tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0.2 nm / sec to a thickness of 30 nm to form an electron injecting and transporting layer. Further, magnesium and silver are further deposited thereon at a deposition rate of 0.2 nm / sec for 200 n.
An organic electroluminescent device was prepared by co-evaporating the resultant to a thickness of 10 m (weight ratio: 10: 1) to form a cathode. In addition, vapor deposition was performed while maintaining the reduced pressure state of the vapor deposition tank. A DC voltage was applied to the produced organic electroluminescent device, and the device was continuously driven at a constant current density of 10 mA / cm ² in a dry atmosphere. Initially, green light emission of 6.2 V and luminance of 460 cd / m ² was confirmed. The half life of the luminance was 1500 hours.

Example 27 A glass substrate having a 200 nm-thick ITO transparent electrode (anode) was ultrasonically cleaned using a neutral detergent, acetone and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, polycarbonate (weight average molecular weight: 50,000),
And the compound of Exemplified Compound No. A-26 by weight ratio of 100:
A hole injection transport layer having a thickness of 40 nm was formed by dip coating using a 3% by weight dichloroethane solution containing 50 parts by weight. Next, after fixing the glass substrate having the hole injecting and transporting layer to a substrate holder of a vapor deposition apparatus, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Next, tris (8-quinolinolato) aluminum was deposited thereon at a deposition rate of 0.2 nm / sec to a thickness of 50 nm to form a light-emitting layer also serving as an electron injection / transport layer. Furthermore, on the light emitting layer,
Magnesium and silver are deposited at a deposition rate of 0.2 nm / sec.
A cathode was formed by co-evaporation (weight ratio: 10: 1) to a thickness of 0 nm to produce an organic electroluminescent device. When a DC voltage of 10 V was applied to the produced organic electroluminescent device in a dry atmosphere, a current of 95 mA / cm ² flowed. Brightness 1030
Green light emission of cd / m ² was confirmed. The half life of the luminance was 250 hours.

Example 28 A glass substrate having a 200-nm-thick ITO transparent electrode (anode) was subjected to ultrasonic cleaning using a neutral detergent, acetone, and ethanol. The substrate was dried using nitrogen gas and further washed with UV / ozone. Next, on the ITO transparent electrode, polymethyl methacrylate (weight average molecular weight 250
00), compound of Exemplified Compound No. B-9, tris (8-
Quinolinolate) aluminum in a weight ratio of 10
Using a 3% by weight dichloroethane solution containing 0: 50: 0.5 in a ratio of 100n by dip coating.
m light emitting layers were formed. Next, after fixing the glass substrate having the light emitting layer to a substrate holder of a vapor deposition device, the pressure in the vapor deposition tank was reduced to 3 × 10 ⁻⁶ Torr. Further, on the light emitting layer, magnesium and silver were co-deposited (weight ratio: 10: 1) to a thickness of 200 nm at a deposition rate of 0.2 nm / sec to form an organic electroluminescent device. When a DC voltage of 15 V was applied to the manufactured organic electroluminescent device in a dry atmosphere, a current of 80 mA / cm ² flowed. Brightness 530
Green light emission of cd / m ² was confirmed. The half life of the luminance was 300 hours.

[0056]

According to the present invention, it has become possible to provide an organic electroluminescent device having a long emission life and excellent durability.

[Brief description of the drawings]

FIG. 1 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 2 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 3 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 4 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 5 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 6 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 7 is a schematic structural diagram of an example of an organic electroluminescent device.

FIG. 8 is a schematic structural diagram of an example of an organic electroluminescent device.

[Explanation of symbols]

 Reference Signs List 1 substrate 2 anode 3 hole injection / transport layer 3a hole injection / transport component 4 light emitting layer 4a light emitting component 5 electron injection / transport layer 5 ″ electron injection / transport layer 5a electron injection / transport component 6 cathode 7 power supply

Claims (4)

[Claims] A compound represented by the general formula (1) between a pair of electrodes:
An organic electroluminescent device comprising at least one layer sandwiching at least one compound containing at least one compound represented by the formula: Embedded image [In the formula, Ar _{1 to} Ar ₄ represent a substituted or unsubstituted aryl group (provided that at least one of Ar _{1 to} Ar ₄ is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, or a substituted Or an unsubstituted biphenyl group), and R ₁ and R ₂ represent a linear, branched or cyclic alkyl group, or a substituted or unsubstituted aralkyl group. 2. The organic electroluminescent device according to claim 1, wherein the layer containing the compound represented by the general formula (1) is a hole injection / transport layer. 3. The organic electroluminescent device according to claim 1, further comprising a light emitting layer between the pair of electrodes. 4. The organic electroluminescent device according to claim 1, further comprising an electron injection / transport layer between the pair of electrodes.