U.S. patent application number 11/344604 was filed with the patent office on 2006-08-24 for organic electrolumescence device.
This patent application is currently assigned to Idemitsu Kosan Co., Ltd.. Invention is credited to Hiromasa Arai, Masakazu Funahashi, Chishio Hosokawa, Hidetsugu Ikeda, Hisayuki Kawamura, Hidetoshi Koga.
Application Number | 20060189828 11/344604 |
Document ID | / |
Family ID | 27527578 |
Filed Date | 2006-08-24 |
United States Patent
Application |
20060189828 |
Kind Code |
A1 |
Hosokawa; Chishio ; et
al. |
August 24, 2006 |
Organic electrolumescence device
Abstract
Materials for organic electroluminescence devices are
represented by following general formula [1]: ##STR1## wherein A
represents a chrysene group, X.sup.1 to X.sup.4 each independently
represent a substituted or unsubstituted arylene group having 6 to
30 carbon atoms, X.sup.1 and X.sup.2 may be bonded to each other,
X.sup.3 and X.sup.4 may be bonded to each other, Y.sup.1 to Y.sup.4
each independently represent an organic group represented by
general formula [2], a to d each represent an integer of 0 to 2
and, a+b+c+d.gtoreq.0; general formula [2] being: ##STR2## wherein
R.sup.1 to R.sup.4 each independently represent hydrogen atom, a
substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, cyano group or form a triple bond by a linkage of
R.sup.1 and R.sup.2 or R.sup.3 and R.sup.4, Z represents a
substituted or unsubstituted aryl group having 6 to 20 carbon atoms
and n represents 0 or 1.
Inventors: |
Hosokawa; Chishio;
(Chiba-ken, JP) ; Funahashi; Masakazu; (Chiba-ken,
JP) ; Kawamura; Hisayuki; (Chiba-ken, JP) ;
Arai; Hiromasa; (Chiba-ken, JP) ; Koga;
Hidetoshi; (Chiba-ken, JP) ; Ikeda; Hidetsugu;
(Chiba-ken, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND, MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Idemitsu Kosan Co., Ltd.
Tokyo
JP
|
Family ID: |
27527578 |
Appl. No.: |
11/344604 |
Filed: |
February 1, 2006 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10814121 |
Apr 1, 2004 |
|
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11344604 |
Feb 1, 2006 |
|
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09623057 |
Aug 25, 2000 |
6743948 |
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PCT/JP99/07390 |
Dec 28, 1999 |
|
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10814121 |
Apr 1, 2004 |
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Current U.S.
Class: |
564/426 ;
257/E51.051; 313/504; 428/917; 564/434 |
Current CPC
Class: |
H05B 33/14 20130101;
C07C 2603/52 20170501; C07C 2603/18 20170501; C07C 2603/24
20170501; C07C 211/61 20130101; C09K 2211/10 20130101; H01L 51/0054
20130101; H01L 51/0058 20130101; H01L 51/0042 20130101; C09B 57/008
20130101; C09K 11/06 20130101; C07C 211/58 20130101; C07C 2603/44
20170501; C09B 57/00 20130101; H01L 2251/308 20130101; C09B 6/00
20130101; C09K 2211/1007 20130101; H01L 51/0061 20130101; H01L
51/0081 20130101; H01L 51/5088 20130101; B01J 31/24 20130101; C09B
3/78 20130101; H01L 51/007 20130101; Y10S 428/917 20130101; C07C
2603/26 20170501; C09B 57/001 20130101; H01L 51/005 20130101; C07C
2603/48 20170501; C09K 2211/1014 20130101; C09B 23/148 20130101;
H01L 51/0068 20130101; H01L 51/006 20130101; C09B 1/00 20130101;
C09K 2211/1092 20130101; H01L 51/5012 20130101; C09K 2211/1011
20130101; C09K 2211/1003 20130101; H01L 51/0052 20130101; H01L
51/0059 20130101; H01L 51/5048 20130101; C07C 211/54 20130101 |
Class at
Publication: |
564/426 ;
564/434; 428/917; 313/504; 257/E51.051 |
International
Class: |
C07C 211/61 20060101
C07C211/61; C09K 11/06 20060101 C09K011/06; H01L 51/54 20060101
H01L051/54 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 28, 1998 |
JP |
373921/1998 |
May 20, 1999 |
JP |
140103/1999 |
Aug 5, 1999 |
JP |
223056/1999 |
Aug 20, 1999 |
JP |
234652/1999 |
Dec 7, 1999 |
JP |
347848/1999 |
Claims
1. A material for an organic electroluminescence device represented
by following general formula (4): ##STR93## wherein X.sup.1 to
X.sup.4 each independently represent a substituted or unsubstituted
arylene group having 6 to 30 carbon atoms, X.sup.1 and X.sup.2 may
be bonded to each other, X.sup.3 and X.sup.4 may be bonded to each
other, Y.sup.1 to Y.sup.4 each independently represent an organic
group represented by general formula (2), a to d each represent an
integer of 0 to 2 with the proviso that a+b+c+d.gtoreq.0; general
formula (2) being: ##STR94## wherein R.sup.1 to R.sup.4 are each
independently a hydrogen atom, a substituted or unsubstituted alkyl
group having 1 to 20 carbon atoms, a substituted or unsubstituted
aryl group having 6 to 20 carbon atoms, cyano group or form a
triple bond by a linkage of R.sup.1 and R.sup.2 or R.sup.3 and
R.sup.4, Z represents a substituted or unsubstituted aryl group
having 6 to 20 carbon atoms and n represents 0 or 1.
2. A dopant material for an organic electroluminescence device
represented by following general formula (4): ##STR95## wherein
X.sup.1 to X.sup.4 each independently represent a substituted or
unsubstituted arylene group having 6 to 30 carbon atoms, X.sup.1
and X.sup.2 may be bonded to each other, X.sup.3 and X.sup.4 may be
bonded to each other, Y.sup.1 to Y.sup.4 each independently
represent an organic group represented by general formula (2), a to
d each represent an integer of 0 to 2 with the proviso that
a+b+c+d.gtoreq.0; general formula (2) being: ##STR96## wherein
R.sup.1 to R.sup.4 are each independently a hydrogen atom, a
substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, cyano group or form a triple bond by a linkage of
R.sup.1 and R.sup.2 or R.sup.3 and R.sup.4, Z represents a
substituted or unsubstituted aryl group having 6 to 20 carbon atoms
and n represents 0 or 1.
3. A hole transporting material for an organic electroluminescence
device represented by following general formula (4): ##STR97##
wherein X.sup.1 to X.sup.4 each independently represent a
substituted or unsubstituted arylene group having 6 to 30 carbon
atoms, X.sup.1 and X.sup.2 may be bonded to each other, X.sup.3 and
X.sup.4 may be bonded to each other, Y.sup.1 to Y.sup.4 each
independently represent an organic group represented by general
formula (2), a to d each represent an integer of 0 to 2 with the
proviso that a+b+c+d.gtoreq.0; general formula (2) being: ##STR98##
wherein R.sup.1 to R.sup.4 are each independently a hydrogen atom,
a substituted or unsubstituted alkyl group having 1 to 20 carbon
atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms, cyano group or form a triple bond by a linkage of
R.sup.1 and R.sup.2 or R.sup.3 and R.sup.4, Z represents a
substituted or unsubstituted aryl group having 6 to 20 carbon atoms
and n represents 0 or 1.
4. The material for an organic electroluminescence device according
to claim 1, wherein in formula (4) a+b+c+c=0.
5. The dopant material for an electroluminescence device according
to claim 2, wherein in formula (4) a+b+c+d=0.
6. The hole transporting material for an electroluminescence device
according to claim 3, wherein in formula (4) a+b+c+d=0.
7. The material for a blue-light emitting organic
electroluminescent device comprising the material of claim 1.
8. The dopant material for a blue-light emitting organic
electroluminescent device comprising the material of claim 2.
9. The hole transporting material for a blue-light emitting organic
electroluminescent device comprising the material of claim 3.
Description
REFERENCE TO PRIOR APPLICATIONS
[0001] This application is a Continuation of U.S. application Ser.
No. 10/814,121, filed Apr. 1, 2004; which is a Division of U.S.
application Ser. No. 09/623,057, now patented; which is a 371 of
PCT/JP99/07390, filed Dec. 28, 1999.
TECHNICAL FIELD
[0002] The present invention relates to materials for organic
electroluminescence devices which are used as a light source such
as a planar light emitting member of televisions and a back light
of displays, exhibit high efficiency of light emission and have
excellent heat resistance and a long life, organic
electroluminescence devices using the materials, novel compounds
and processes for producing materials for electroluminescence
devices.
BACKGROUND ART
[0003] Electroluminescence (EL) devices using organic compounds are
expected to be used for inexpensive full color display devices of
the solid light emission type which can display a large area and
development thereof has been actively conducted. In general, an EL
device is constituted with a light emitting layer and a pair of
electrodes faced to each other at both sides of the light emitting
layer. When a voltage is applied between the electrodes, electrons
are injected at the side of the cathode and holes are injected at
the side of the anode. The electrons are combined with the holes in
the light emitting layer and an excited state is formed. When the
excited state returns to the normal state, the energy is emitted as
light.
[0004] Heretofore, organic EL devices require higher driving
voltages and show inferior luminance of emitted light and inferior
efficiencies of light emission in comparison with inorganic
devices. Moreover, properties of organic EL devices deteriorate
very rapidly. Therefore, heretofore, organic EL devices have not
been used practically. Although the properties of organic EL
devices have been improved, organic EL devices exhibiting a
sufficient efficiency of light emission and having sufficient heat
resistance and life have not been obtained. For example, a
phenylanthracene derivative which can be used for EL devices is
disclosed in Japanese Patent Application Laid-Open No. Heisei
8(1996)-12600. However, an organic EL device using this compound
exhibited an efficiency of light emission as low as about 2 to 4
cd/A and improvement in the efficiency is desired. In Japanese
Patent Application Laid-Open No. Heisei 8(1996)-199162, an EL
device having a light emitting layer containing a fluorescent
dopant of a derivative of an amine or a diamine is disclosed.
However, this EL device has a life as short as 700 hours at an
initial luminance of emitted light of 300 cd/m.sup.2 although the
efficiency of light emission is 4 to 6 dc/A and improvement in the
life is desired. In Japanese Patent Application Laid-Open No.
Heisei 9(1997)-268284, a material for EL devices having
phenylanthracene group is disclosed. This material exhibits a
marked decrease in the luminance of emitted light when the material
is used at a high temperature for a long time and heat resistance
is insufficient. Moreover, these devices do not emit light in the
region of orange to red color. Since emission of red color is
indispensable for the full color display by an EL device, a device
emitting light in the region of orange to red color is desired.
When these materials are used as the host material and other
compounds are used as the doping material, a long life cannot be
obtained. It is necessary for practical use that an initial
luminance of emitted light of 10,000 d/m.sup.2 or greater be
exhibited. However, this value has not been achieved. In Japanese
Patent Application Laid-Open No. Heisei 11(1999)-152253, an example
is disclosed in which a material for organic EL devices having a
binaphthalene structure is added to a light emitting layer having
the property to transfer electrons such as a layer of an aluminum
complex or the like. However, in this example, the aluminum complex
or the like emits light and the material for organic EL devices
does not function as the light emitting center since the energy gap
of the light emitting layer of the aluminum complex or the like is
smaller than the energy gap of the material for organic EL
devices.
[0005] Synthesis of arylamines used as a material for organic EL
devices has been conducted by the Ullmann reaction using an amine
and an iodobenzene. It is described, for example, in Chem. Lett.,
pp. 1145 to 1148, 1989; the specification of U.S. Pat. No.
4,764,625; and Japanese Patent Application Laid-Open No. Heisei
8(1996)-48974 that a triarylamine is produced by the reaction of a
corresponding iodobenzene and a diarylamine in an inert hydrocarbon
solvent such as decaline at 150.degree. C. or higher in the
presence of one equivalent or more of copper powder and a base such
as potassium hydroxide as the typical example.
[0006] However, the process using the Ullmann reaction has
drawbacks in that an expensive iodide must be used as the reacting
agent, that the reaction cannot be applied to many types of
compounds, that the yield of the reaction is not sufficient, that
the reaction requires a temperature as high as 150.degree. C. and a
long time and that waste liquid containing a great amount of copper
is formed since copper powder is used in a great amount and
environmental problems arise.
DISCLOSURE OF THE INVENTION
[0007] The present invention has been made to overcome the above
problems and has an object to provide a material for organic
electroluminescence devices, an organic electroluminescence device
and a novel compound which exhibit high efficiency of light
emission and have a long life and excellent heat resistance and a
process for producing the material for organic electroluminescence
devices.
[0008] As the result of extensive studies by the present inventors
to develop the material for organic EL devices having the
advantageous properties described above and an organic EL device
using the material, it was found that the object can be achieved by
using the compounds represented by general formulae [1] and [3] to
[10] which are shown below. The present invention has been
completed based on this knowledge.
[0009] It was also found by the present inventors that the above
object can be achieved by using the compounds represented by
general formulae [11] and [11'] as the doping material or the light
emitting center.
[0010] It was further found by the present inventors that a
tertiary arylamine which is a material for organic EL devices can
be synthesized with a high activity by the reaction of an amine and
an aryl halide in the presence of a catalyst comprising a phosphine
compound and a palladium compound and a base. The present invention
has been completed based on the above knowledge.
[0011] The material for organic electroluminescence devices
(referred to as the material for organic EL devices) of the present
invention is a compound represented by following general formula
[1]: ##STR3## wherein A represents a substituted or unsubstituted
arylene group having 22 to 60 carbon atoms, X.sup.1 to X.sup.4 each
independently represent a substituted or unsubstituted arylene
group having 6 to 30 carbon atoms, X.sup.1 and X.sup.2 may be
bonded to each other, X.sup.3 and X.sup.4 may be bonded to each
other, Y.sup.1 to Y.sup.4 each independently represent an organic
group represented by general formula [2], a to d each represent an
integer of 0 to 2 and, when the arylene group represented by A has
26 or less carbon atoms, a+b+c+d>0 and the arylene group does
not contain two or more anthracene nuclei; general formula [2]
being: ##STR4## wherein R.sup.1 to R.sup.4 each independently
represent hydrogen atom, a substituted or unsubstituted alkyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms or cyano group or form a triple
bond by a linkage of R.sup.1 and R.sup.2 or R.sup.3 and R.sup.4, Z
represents a substituted or unsubstituted aryl group having 6 to 20
carbon atoms and n represents 0 or 1.
[0012] The material for organic electroluminescence devices of the
present invention may also be a compound represented by following
general formula [3]: ##STR5## wherein B represents a substituted or
unsubstituted arylene group having 6 to 60 carbon atoms, X.sup.1 to
X.sup.4 each independently represent a substituted or unsubstituted
arylene group having 6 to 30 carbon atoms, X.sup.1 and X.sup.2 may
be bonded to each other, X.sup.3 and X.sup.4 may be bonded to each
other, Y.sup.1 to Y.sup.4 each independently represent an organic
group represented by general formula [2] described above, a to d
each represent an integer of 0 to 2 and at least one of groups
represented by B, X.sup.1, X.sup.2, X.sup.3 and X.sup.4 has a
chrysene nucleus.
[0013] It is preferable that general formula [3] means following
general formula [4], general formula [5] or general formula [6].
##STR6## wherein X.sup.1 to X.sup.4, Y.sup.1 to Y.sup.4 and a to d
are each independently the same as those in general formula [3].
##STR7## wherein B, X.sup.1, X.sup.2, Y.sup.1, Y.sup.2, a and b are
each independently the same as those in general formula [3].
##STR8## wherein B, X.sup.1, X.sup.2, Y.sup.1, Y.sup.2, a and b are
each independently the same as those in general formula [3].
[0014] The material for organic electroluminescence devices of the
present invention may also be a compound represented by following
general formula [7]: ##STR9## wherein D represents a divalent group
having a tetracene nucleus or a pentacene nucleus, X.sup.1 to
X.sup.4 each independently represent a substituted or unsubstituted
arylene group containing 6 to 30 carbon atoms, X.sup.1 and X.sup.2
may be bonded to each other, X.sup.3 and X.sup.4 may be bonded to
each other, Y.sup.1 to Y.sup.4 each independently represent an
organic group represented by general formula [2] described above
and a to d each represent an integer of 0 to 2.
[0015] It is preferable that general formula [7] means following
general formula [8]: ##STR10## wherein X.sup.1 to X.sup.4, Y.sup.1
to Y.sup.4 and a to d are each independently the same as those in
general formula [7], R.sup.51 to R.sup.60 each independently
represent hydrogen atom, a substituted or unsubstituted alkyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy
group having 1 to 20 carbon atoms, a substituted or unsubstituted
aryl group having 6 to 20 carbon atoms or cyano group and adjacent
groups among the groups represented by R.sup.51 to R.sup.60 may be
bonded to each other to form a saturated or unsaturated and
substituted or unsubstituted carbon ring.
[0016] The material for organic electroluminescence devices of the
present invention may also be a compound represented by following
general formula [9]: ##STR11## wherein E represents a divalent
group comprising an anthracene nucleus which is substituted with
aryl groups or unsubstituted, X.sup.5 to X.sup.8 each independently
represent a substituted or unsubstituted arylene group having 6 to
20 carbon atoms, X.sup.5 and X.sup.6 may be bonded to each other,
X.sup.7 and X.sup.8 may be bonded to each other, Y.sup.1 to Y.sup.4
each independently represent an organic group represented by
general formula [2], a to d each represent an integer of 0 to 2,
and when the group represented by E is an unsubstituted group:
##STR12## at least two of X.sup.5 to X.sup.8 contains a substituted
or unsubstituted group: ##STR13##
[0017] The material for organic electroluminescence devices of the
present invention may also be a compound represented by following
general formula [10]: ##STR14## wherein Ar.sup.1 and Ar.sup.3 each
independently represents a divalent group selected from a group
consisting of substituted and unsubstituted phenylene groups,
substituted and unsubstituted 1,3-naphthalene groups, substituted
and unsubstituted 1,8-naphthalene groups, substituted and
unsubstituted fluorene groups and substituted and unsubstituted
biphenyl groups, Ar.sup.2 represents a divalent group selected from
a group consisting of substituted and unsubstituted anthracene
nuclei, substituted and unsubstituted pyrene nuclei, substituted
and unsubstituted phenanthrene nuclei, substituted and
unsubstituted chrysene nuclei, substituted and unsubstituted
pentacene nuclei, substituted and unsubstituted naphthacene nuclei
and substituted and unsubstituted fluorene nuclei, X.sup.5 to
X.sup.8 each independently represent a substituted or unsubstituted
arylene group having 6 to 20 carbon atoms, X.sup.5 and X.sup.6 may
be bonded to each other, X.sup.7 and X.sup.8 may be bonded to each
other, Y.sup.1 to Y.sup.4 each independently represent an organic
group represented by general formula [2] described above, a to d
each represent an integer of 0 to 2, a+b+c+d.ltoreq.2, e represents
0 or 1, f represents 1 or 2 and, when Ar.sup.2 represents an
anthracene nucleus, a case in which a=b=c=d and Ar.sup.1 and
Ar.sup.3 both represent p-phenylene group is excluded.
[0018] The material for organic electroluminescence devices of the
present invention may also be a compound represented by following
general formula [11]: ##STR15## wherein F represents a substituted
or unsubstituted arylene group having 6 to 21 carbon atoms, X.sup.1
to X.sup.4 each independently represent a substituted or
unsubstituted arylene group having 6 to 30 carbon atoms, X.sup.1
and X.sup.2 may be bonded to each other, X.sup.3 and X.sup.4 may be
bonded to each other, Y.sup.1 to Y.sup.4 each independently
represent an organic group represented by general formula [2]
described above, a to d each represent an integer of 0 to 2, and
a+b+c+d>0.
[0019] It is preferable that the group represented by F in general
formula [11] is a group represented by following general formula
[12], general formula [13] or general formula [14]: ##STR16##
##STR17## wherein R.sup.5' to R.sup.24' each independently
represent hydrogen atom, a substituted or unsubstituted alkyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms or cyano group and adjacent
groups among the groups represented by R.sup.5' to R.sup.24' my be
bonded to each other to form a saturated or unsaturated carbon
ring; ##STR18## wherein R.sup.25' to R.sup.34' each independently
represent hydrogen atom, a substituted or unsubstituted alkyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms or cyano group and adjacent
groups among the groups represented by R.sup.5' to R.sup.24' my be
bonded to each other to form a saturated or unsaturated carbon
ring.
[0020] The material for organic EL devices of the present invention
which is represented by any of general formulae [1], [3] to [11]
and [11'] can be used also as the light emitting material for
organic electroluminescence devices.
[0021] The organic electroluminescence (EL) device of the present
invention comprises a light emitting layer or a plurality of thin
films of organic compounds comprising a light emitting layer
disposed between a pair of electrodes, wherein at least one of the
thin films of organic compounds is a layer comprising a materials
for organic EL devices represented by any of general formulae [1],
[3] to [11] and [11'].
[0022] It is preferable that, in the above organic EL device, a
layer comprising the material for organic EL devices represented by
any of general formulae [1], [3] to [11] and [11'] as at least one
material selected from a group consisting of a hole injecting
material, a hole transporting material and a doping material is
disposed between the pair of electrodes
[0023] It is preferable that, in the above organic EL device, the
light emitting layer comprises 0.1 to 20% by weight of a material
for organic EL devices represented by any of general formulae [1],
[3] to [11] and [11'].
[0024] It is preferable that, in the above organic
electroluminescence device, one or more materials selected from a
group consisting of a hole injecting material, a hole transporting
material and a doping material each independently comprise 0.1 to
20% by weight of the material for organic EL devices represented by
any of general formulae [1], [3] to [11] and [11'].
[0025] It is preferable that, in the above organic EL device, the
light emitting layer is a layer comprising a stilbene derivative
and a material for organic EL devices represented by any of general
formulae [1], [3] to [11] and [11'].
[0026] In the above organic EL device, a layer comprising an
aromatic tertiary amine derivative and/or a phthalocyanine
derivative is disposed between a light emitting layer and an
anode.
[0027] It is preferable that, in the above organic EL device, the
energy gap of the material for organic electroluminescence devices
represented by general formula [11] is smaller than the energy gap
of a host material by 0.07 eV or greater.
[0028] The novel compound of the present invention is represented
by following general formula [11']: ##STR19## wherein F represents
a group represented by general formula [14], X.sup.1 to X.sup.4
each independently represent a substituted or unsubstituted arylene
group having 6 to 30 carbon atoms, X.sup.1 and X.sup.2 may be
bonded to each other, X.sup.3 and X.sup.4 may be bonded to each
other, Y.sup.1 to Y.sup.4 each independently represent an organic
group represented by general formula [2] described above, a to d
represent each an integer of 0 to 2, and a+b+c+d>0; general
formula [14] being: ##STR20## wherein R.sup.25' to R.sup.34' each
independently represent hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted aryl group having 6 to 20 carbon atoms
or cyano group and adjacent groups among the groups represented by
R.sup.5' to R.sup.24' my be bonded to each other to form a
saturated or unsaturated carbon ring.
[0029] The process for producing a material for organic EL devices
of the present invention comprises reacting, in a presence of a
catalyst comprising a phosphine compound and a palladium compound
and a base, a primary amine or a secondary amine represented by
following general formula [15]: R(NR'H).sub.k [15] wherein k
represents an integer of 1 to 3; when k represents 1, R and R'
represent hydrogen atom, an alkyl group or a substituted or
unsubstituted aryl group; and when k represents 2 or 3, R
represents an alkylene group or substituted or unsubstituted
arylene group and R' represents hydrogen atom, an alkyl group or a
substituted or unsubstituted aryl group, with an aryl halide
represented by following general formula [16]: Ar(X).sub.m [16]
wherein Ar represents a substituted or unsubstituted aryl group, X
represents F, Cl, Br or I and m represents an integer of 1 to 3,
and producing a material for organic electroluminescence devices
comprising an arylamine compound.
[0030] It is preferable that the arylamine described above is a
compound represented by following general formula [17]: ##STR21##
wherein F represents a substituted or unsubstituted arylene group
having 6 to 60 carbon atoms, X.sup.1 to X.sup.4 each independently
represent a substituted or unsubstituted arylene group having 6 to
30 carbon atoms, X.sup.1 and X.sup.2 may be bonded to each other,
X.sup.3 and X.sup.4 may be bonded to each other, Y.sup.1 to Y.sup.4
each independently represent an organic group represented by
general formula [2] described above, a to d each represent an
integer of 0 to 2, and a+b+c+d>0.
[0031] It is preferable that the phosphine compound is a
trialkylphosphine compound, a triarylphosphine compound or a
diphosphine compound.
BRIEF DESCRIPTION OF THE DRAWINGS
[0032] FIG. 1 shows a .sup.1H.sub.NMR chart of compound a
synthesized in accordance with the process of the present
invention.
[0033] FIG. 2 shows a .sup.1H.sub.NMR chart of compound b
synthesized in accordance with the process of the present
invention.
[0034] FIG. 3 shows a .sup.1H.sub.NMR chart of compound e
synthesized in accordance with the process of the present
invention.
THE MOST PREFERRED EMBODIMENT TO CARRY OUT THE INVENTION
[0035] In general formula [1] in the present invention, A
represents a substituted or unsubstituted arylene group having 22
to 60 carbon atoms. Examples of the arylene group include divalent
groups formed from biphenyl, terphenyl, naphthalene, anthracene,
phenanthrene, pyrene, fluorene, thiophene, coronene and
fluoranthene and divalent groups formed by bonding a plurality of
these groups to each other. X.sup.1 to X.sup.4 in general formula
[1] each independently represent a substituted or unsubstituted
arylene group having 6 to 30 carbon atoms. Examples of the group
represented by X.sup.1 to X.sup.4 include monovalent or divalent
groups containing skeleton structures of phenyl, biphenyl,
terphenyl, naphthalene, anthrathene, phenanthrene, pyrene,
fluorene, thiophene, coronene and chrysene. X.sup.1 and X.sup.2 may
be connected to each other and X.sup.3 and X.sup.4 may be connected
to each other.
[0036] The groups used as the substituents to the groups
represented by X.sup.1 to X.sup.4 are each independently an alkyl
group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20
carbon atoms or an aryl group having 6 to 20 carbon atoms. Aryloxy
groups, arylthio groups, arylalkyl groups and aryl ketone groups
are excluded from the above substituent because compounds having
the groups excluded above tend to decompose under heating in vapor
deposition and the life of the obtained device is short.
[0037] In general formula [1], a to d each represent an integer of
0 to 2. However, when the group represented by A has 26 or less
carbon atoms, a+b+c+d>0 and the group represented by A does not
contain 2 or more anthracene nuclei.
[0038] In general formula [2] in the present invention, R.sup.1 to
R.sup.4 each independently represent hydrogen atom, a substituted
or unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted aryl group having 6 to 20 carbon atoms
or cyano group. Examples of the group represented by R.sup.1 to
R.sup.4 include substituted and unsubstituted alkyl groups such as
methyl group, ethyl group, propyl group, butyl group, sec-butyl
group, tert-butyl group, pentyl group, hexyl group, heptyl group,
octyl group, stearyl group, 2-phenylisopropyl group,
trichloromethyl group, trifluoromethyl group, benzyl group,
.alpha.-phenoxybenzyl group, .alpha.,.alpha.-dimethylbenzyl group,
.alpha.,.alpha.-methylphenylbenzyl group,
.alpha.,.alpha.-ditrifluoromethylbenzyl group, triphenylmethyl
group and .alpha.-benzyloxybenzyl group; and substituted and
unsubstituted aryl groups such as phenyl group, 2-methylphenyl
group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl
group, biphenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl
group, 4-cyclohexylbiphenyl group, terphenyl group,
3,5-dichlorophenyl group, naphthyl group, 5-methylnaphthyl group,
anthryl group and pyrenyl group.
[0039] In general formula [2] in the present invention, Z
represents a substituted or unsubstituted aryl group having 6 to 20
carbon atoms. Examples of the group represented by Z include aryl
groups such as phenyl group, biphenyl group, terphenyl group,
naphthyl group, anthryl group, phenanthryl group, fluorenyl group,
pyrenyl group and thiophene group. The above aryl groups may have
substituents. Examples of the substituent include alkyl groups and
aryl groups described above as the examples of the group
represented by R.sup.1 to R.sup.4, alkoxy groups, amino group,
cyano group, hydroxyl group, carboxylic acid group, ether group and
ester groups. In general formula [2], n represents 0 or 1.
[0040] As described above, since the compound represented by
general formula [1] in the present invention has a diamine
structure at the central portion and a styrylamine structure at end
portions, the ionization energy is 5.6 eV or smaller and holes can
be easily injected. The mobility of holes is 10.sup.-4 m.sup.2/Vs
or greater. Therefore, the compound has the excellent properties as
the hole injecting material and the hole transporting material. Due
to the polyphenyl structure at the center, the electron affinity is
2.5 eV or greater and electrons can be easily injected.
[0041] Moreover, since the structure represented by A has 22 or
more carbon atoms, an amorphous thin film can be easily formed. The
glass transition temperature is raised to 100.degree. C. or higher
and heat resistance can be improved. When two or more anthracene
groups are contained in the structure represented by A, there is
the possibility that the compound represented by general formula
[1] decomposes under heating.
[0042] Compounds having a structure in which X.sup.1 and X.sup.2 or
X.sup.3 and X.sup.4 are bonded to each other through a single bond
or a carbon ring bond has elevated glass transition temperatures
and show improved heat resistance.
[0043] In the compounds represented by general formulae [3] to [6]
of the present invention, B represents a substituted or
unsubstituted arylene group having 6 to 60 carbon atoms. Examples
of the group represented by B include divalent groups formed from
biphenyl, terphenyl, naphthalene, anthracene, phenanthrene, pyrene,
fluorene, thiophene, coronene and fluoranthene and divalent groups
formed by bonding a plurality of these groups to each other.
X.sup.1 to X.sup.4, Y.sup.1 to Y.sup.4 and a to d are the same as
those in general formula [1], wherein at least one of the groups
represented by B, X.sup.1, X.sup.2, X.sup.3 and X.sup.4 has a
chrysene nucleus.
[0044] As described above, since the compounds represented by
general formulae [3] to [6] in the present invention have a diamine
structure at the central portion and a styrylamine structure at end
portions, the ionization energy is 5.6 eV or smaller and holes can
be easily injected. The mobility of holes is 10.sup.-4 m.sup.2/Vs
or greater. Therefore, the compound has the excellent properties as
the hole injecting material and the hole transporting material. Due
to the chrysene nucleus contained in at least one of the groups
represented by B, X.sup.1, X.sup.2, X.sup.3 and X.sup.4, durability
and heat resistance are improved. Therefore, driving for a long
time is enabled and an organic EL device which can be stored or
driven at high temperatures can be obtained.
[0045] Moreover, the life of the organic EL device can be extended
when the compounds represented by general formulae [3] to [6] are
used as the doping material and the efficiency of light emission
can be improved when the compounds are used as the material of the
light emitting layer.
[0046] In the compound represented by general formula [7] of the
present invention, D represents a divalent group containing a
substituted or unsubstituted tetracene nucleus or pentacene
nucleus. Examples of the group represented by D include divalent
groups formed by connecting a plurality of at least one group
selected from the group consisting of biphenyl, naphthalene,
anthracene, phenanthrene, fluorene and thiophene and the tetracene
nucleus or the pentacene nucleus. X.sup.1 to X.sup.4, Y.sup.1 to
Y.sup.4 and a to d are the same as those in general formula [1],
wherein X.sup.1 and X.sup.2 may be bonded to each other and X.sup.3
and X.sup.4 may be bonded to each other.
[0047] In the compound represented by general formula [8] of the
present invention, X.sup.1 to X.sup.4, Y.sup.1 to Y.sup.4 and a to
d each independently represent the same atom and groups as those
described above in general formula [1]. R.sup.51 to R.sup.60 each
independently represent hydrogen atom, a substituted or
unsubstituted alkyl group having 1 to 20 carbon atoms, a
substituted or unsubstituted alkoxy group having 1 to 20 carbon
atoms, a substituted or unsubstituted aryl group having 6 to 20
carbon atoms or cyano group and adjacent groups among the groups
represented by R.sup.51 to R.sup.60 may be bonded to each other to
form a saturated or unsaturated and substituted or unsubstituted
carbon ring.
[0048] The groups used as the substituent in general formulae [7]
and [8] are each independently an alkyl group having 1 to 20 carbon
atoms, an alkoxy group having 1 to 20 carbon atoms or an aryl group
having 6 to 20 carbon atoms. Aryloxy groups, arylthio groups,
arylalkyl groups and aryl ketone groups are excluded from the above
substituent because compounds having the groups excluded above tend
to decompose under heating in vapor deposition and the life of the
obtained device is short.
[0049] As described above, the compound represented by general
formula [7] in the present invention exhibits strong fluorescence
in the region of orange to red color due to the tetracene or
pentacene structure. Holes are easily injected due to the diamine
structure. When this compound is contained in the light emitting
layer, holes are easily trapped and recombination of electrons and
holes is promoted. Therefore, a light emitting device emitting
yellow color, orange color and red color in a high efficiency can
be obtained.
[0050] In particular, when the compound represented by general
formula [7] is used as the doping material, the obtained light
emitting device has a long life and exhibits more excellent
stability than that exhibited by any conventional devices.
[0051] In the compound represented by general formula [9] in the
present invention, E represents a divalent group comprising an
anthracene nucleus which is substituted with aryl groups or
unsubstituted. X.sup.5 to X.sup.8 each independently represent a
substituted or unsubstituted arylene group having 6 to 20 carbon
atoms. Examples of the group represented by X.sup.5 to X.sup.8
include monovalent and divalent groups containing the skeleton
structure of phenylene, biphenyl, terphenyl, naphthalene,
anthracene, phenanthrene, fluorene and thiophene. X.sup.5 and
X.sup.6 may be bonded to each other and X.sup.7 and X.sup.8 may be
bonded to each other. Y.sup.1 to Y.sup.4 and a to d are the same as
those in general formula [1].
[0052] However, when E represents an unsubstituted group: ##STR22##
at least two of X.sup.5 to X.sup.8 contain a substituted or
unsubstituted group: ##STR23##
[0053] As described above, since the compound represented by
general formula [9] in the present invention has a diamine
structure, the ionization energy is 5.6 eV or smaller and holes can
be easily injected. The mobility of holes is 10.sup.-4 m.sup.2/Vs
or greater. Therefore, the compound has the excellent properties as
the hole injecting material and the hole transporting material. Due
to the substituted or unsubstituted anthracene nucleus at the
center, electrons are easily injected.
[0054] When the anthracene nucleus represented by E is
unsubstituted, the glass transition temperature is as low as
100.degree. C. or lower. The glass transition temperature can be
elevated by bonding at least two substituents and preferably 2 to 4
substituents to the nucleus as described above. The specific
biphenyl structure described above enhances solubility of the
compound represented by general formula [9] and purification can be
facilitated. When phenyl group is bonded at a position other than
the above position, i.e., at the para-position, the content of
impurities increases since purification becomes difficult and the
properties of the obtained organic EL device deteriorate. By the
substitution of aryl groups as described above, formation of pairs
of the molecules by association is suppressed and the quantum
efficiency of fluorescence emission increases. Thus, the efficiency
of light emission of the organic EL device is improved.
[0055] In the compound represented by general formula [10] in the
present invention, Ar.sup.1 and Ar.sup.3 each independently
represents a divalent group selected from the group consisting of
substituted and unsubstituted phenylene groups, substituted and
unsubstituted 1,3-naphthalene groups, substituted and unsubstituted
1,8-naphthalene groups, substituted and unsubstituted fluorene
groups and substituted and unsubstituted biphenyl groups, Ar.sup.2
represents a divalent group selected from the group consisting of
substituted and unsubstituted anthracene nuclei, substituted and
unsubstituted pyrene nuclei, substituted and unsubstituted
phenanthrene nuclei, substituted and unsubstituted chrysene nuclei,
substituted and unsubstituted pentacene nuclei, substituted and
unsubstituted naphthacene nuclei and substituted and unsubstituted
fluorene nuclei. Examples of the divalent group include: ##STR24##
##STR25## ##STR26## ##STR27##
[0056] X.sup.5 to X.sup.8 and Y.sup.1 to Y.sup.4 each independently
represent the same groups as those described in general formula
[9]. a to d each represent an integer of 0 to 2, a+b+c+d.ltoreq.2,
e represents 0 or 1 and f represents 1 or 2, wherein, when Ar.sup.2
represents an anthracene nucleus, the case in which a=b=c=d and
Ar.sup.1 and Ar.sup.3 both represent p-phenylene group is
excluded.
[0057] As described above, since the compound represented by
general formula [10] in the present invention has a diamine
structure, the ionization energy is 5.6 eV or smaller and holes can
be easily injected. The mobility of holes is 10.sup.-4 m.sup.2/Vs
or greater. Therefore, the compound has the excellent properties as
the hole injecting material and the hole transporting material, in
particular as the light emitting material. Due to the polyphenyl
structure of the compound having the condensed ring at the center,
electrons can be easily injected.
[0058] Since the compound has both of the polyphenyl structure and
the diamine structure, a stable amorphous thin film can be formed
and exhibits excellent heat resistance due to the glass transition
temperature of 100.degree. C. or higher. When the compound contains
two or more structures represented by general formula [2], the
condition of a+b+c+d.ltoreq.2 is required because the compound
decomposes under heating in vapor deposition for formation of the
thin film. When Ar.sup.2 represents an anthracene nucleus,
decomposition under heating and oxidation in vapor deposition can
be prevented by the above specific structures of Ar.sup.1 and
Ar.sup.3.
[0059] In the compounds represented by general formulae [11] and
[11'] in the material for the organic EL devices and the novel
compound used in the organic EL device of the present invention, F
represents a substituted or unsubstituted arylene group having 6 to
21 carbon atoms. Examples of the group represented by F include
divalent groups formed from biphenyl, terphenyl, naphthalene,
anthracene, phenanthrene, pyrene, fluorene, thiophene and
fluoranthene.
[0060] In general formulae [11] and [11'], a to d each represent an
integer of 0 to 2, wherein a+b+c+d>0.
[0061] As described above, since the compounds represented by
general formulae [11] and [11'] in the present invention have a
diamine structure at the center and a styrylamine structure at end
portions, the ionization energy is 5.6 eV or smaller. Therefore,
the property of injecting holes into the light emitting layer is
improved by adding the compound into the light emitting layer.
Moreover, the balance between electrons and holes in the light
emitting layer is improved by catching holes and the efficiency of
light emission and the life are improved. The efficiency of light
emission and the life are improved in comparison with the case in
which the light emitting layer is composed of the above compound
represented by general formula [11] or [11'] alone as the sole
material for the organic EL material The compound having the
structure in which X.sup.1 and X.sup.2 are bonded to each other and
X.sup.3 and X.sup.4 are bonded to each other through a single bond
or through a carbon ring bond provides an elevated glass transition
temperature and improved heat resistance.
[0062] In the group represented by general formulae [12] to [14] in
the present invention, R.sup.5' to R.sup.34' each independently
represent hydrogen atom, a substituted or unsubstituted alkyl group
having 1 to 20 carbon atoms, a substituted or unsubstituted aryl
group having 6 to 20 carbon atoms or cyano group and adjacent
groups among the groups represented by R.sup.5' to R.sup.24' may be
bonded to each other to form a saturated or unsaturated carbon
ring. Examples of the group represented by R.sup.5' to R.sup.34'
include substituted and unsubstituted alkyl groups such as methyl
group, ethyl group, propyl group, butyl group, sec-butyl group,
tert-butyl group, pentyl group, hexyl group, heptyl group, octyl
group, stearyl group, 2-phenylisopropyl group, trichloromethyl
group, trifluoromethyl group, benzyl group, .alpha.-phenoxybenzyl
group, .alpha.,.alpha.-dimethylbenzyl group,
.alpha.,.alpha.-methylphenylbenzyl group,
.alpha.,.alpha.-ditrifluoromethylbenzyl group, triphenylmethyl
group and .alpha.-benzyloxybenzyl group; and substituted and
unsubstituted aryl groups such as phenyl group, 2-methylphenyl
group, 3-methylphenyl group, 4-methylphenyl group, 4-ethylphenyl
group, biphenyl group, 4-methylbiphenyl group, 4-ethylbiphenyl
group, 4-cyclohexylbiphenyl group, terphenyl group,
3,5-dichlorophenyl group, naphthyl group, 5-methylnaphthyl group,
anthryl group and pyrenyl group.
[0063] In the following, Compounds (1) to (28) as the typical
examples of the compound represented by general formula [1],
Compounds (29) to (56) as the typical examples of the compounds
represented by general formulae [3] to [6], Compounds (57) to (74)
as the typical examples of the compound represented by general
formula [7], Compounds (75) to (86) as the typical examples of the
compound represented by general formula [8], Compounds (87) to
(104) as the typical examples of the compound represented by
general formula [9], Compounds (105) to (126) as the typical
examples of the compound represented by general formula [10] and
Compounds (127) to (141) as the typical examples of the compounds
represented by general formulae [11] and [11'] are shown. However,
the present invention is not limited to these typical examples.
##STR28## ##STR29## ##STR30## ##STR31## ##STR32## ##STR33##
##STR34## ##STR35## ##STR36## ##STR37## ##STR38## ##STR39##
##STR40## ##STR41## ##STR42## ##STR43## ##STR44## ##STR45##
##STR46## ##STR47## ##STR48## ##STR49## ##STR50## ##STR51##
##STR52## ##STR53## ##STR54## ##STR55##
[0064] The compounds represented by general formulae [1], [3] to
[10] of the present invention exhibit strong fluorescence in the
solid state, have the excellent light emitting property in the
electric field and show a quantum efficiency of fluorescence
emission of 0.3 or greater since the polyphenyl structure
represented by A or B and the amine structure are connected to each
other at the center of the compounds. The compounds represented by
general formulae [7] and [8] exhibit strong fluorescence in the
solid state or the dispersed state in the fluorescence region of
yellow color, orange color or red color and have an excellent light
emitting property in the electric field since the structure
containing the tetracene nucleus or the pentacene nucleus and the
amine structure are connected to each other.
[0065] The compounds represented by general formulae [1], [3] to
[10] of the present invention can be used effectively as the light
emitting material and may be used also as the hole transporting
material, the electron transporting material and the doping
material since the compounds have all of the hole injecting
property from metal electrodes or organic thin film layers, the
hole transporting property, the electron injecting property from
metal electrodes or organic thin film layers and the electron
transporting property. In particular, when the compounds
represented by general formula [7] and [8] are used as the doping
material, highly efficient emission of red light can be achieved
since the compounds works as the center of recombination of
electrons and holes.
[0066] The compound represented by general formula [8] exhibits a
particularly excellent property since the arylamine and tetracene
are bonded at the specific positions.
[0067] The organic EL device of the present invention is a device
in which one or a plurality of organic thin films are disposed
between an anode and a cathode. When the device has a single layer,
a light emitting layer is disposed between an anode and a cathode.
The light emitting layer contains a light emitting material and may
also contain a hole injecting material or a electron injecting
material to transport holes injected at the anode or electrons
injected at the cathode to the light emitting material. However, it
is possible that the light emitting layer is formed with the light
emitting material of the present invention alone because the light
emitting material of the present invention has a very high quantum
efficiency of fluorescence emission, excellent ability to transfer
holes and excellent ability to transfer electrons and a uniform
thin film can be formed. The organic EL device of the present
invention having a multi-layer structure has a laminate structure
such as: (an anode/a hole injecting layer/a light emitting layer/a
cathode), (an anode/a light emitting layer/an electron injecting
layer/a cathode) and (an anode/a hole injecting layer/a light
emitting layer/an electron injecting layer/a cathode). Since the
compounds represented by general formulae [1], [3] to [11], [11']
and [17] have the excellent light emitting property and, moreover,
the excellent hole injecting property, hole transporting property,
electron injecting property and electron transporting property, the
compounds can be used for the light emitting layer as the light
emitting material.
[0068] In the light emitting layer, where necessary, conventional
light emitting materials, doping materials, hole injecting
materials and electron injecting materials may be used in addition
to the compounds represented by general formulae [1], [3] to [11],
[11'] and [17] of the present invention. Deterioration in luminance
and life caused by quenching can be prevented by the multi-layer
structure of the organic EL. Where necessary, a light emitting
materials, a doping materials, a hole injecting materials and an
electron injecting materials may be used in combination. By using a
doping material, luminance and the efficiency of light emission can
be improved and blue light and red light can be emitted. The hole
injecting layer, the light emitting layer and the electron
injecting layer may each have a multi-layer structure having two or
more layers. When the hole injecting layer has a multi-layer
structure, the layer into which holes are injected from the
electrode is referred to as the hole injecting layer and the layer
which receives holes from the hole injecting layer and transports
holes from the hole injecting layer to the light emitting layer is
referred to as the hole transporting layer. When the electron
injecting layer has a multi-layer structure, the layer into which
electrons are injected from the electrode is referred to as the
electron injecting layer and the layer which receives electrons
from the electron injecting layer and transports electrons from the
electron injecting layer to the light emitting layer is referred to
as the electron transporting layer. These layers are each selected
and used in accordance with factors such as the energy level and
heat resistance of the material and adhesion with the organic
layers or the metal electrodes.
[0069] Examples of the material which can be used in the light
emitting layer as the light emitting material or the doping
material in combination with the compounds represented by general
formulae [1], [3] to [11], [11'] and [17] include anthracene,
naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene,
fluoresceine, perylene, phthaloperylene, naphthaloperylene,
perynone, phthaloperynone, naphthaloperynone, diphenylbutadiene,
tetraphenylbutadiene, coumarine, oxadiazole, aldazine,
bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, metal
complexes of quinoline, metal complexes of aminoquinoline, metal
complexes of benzoquinoline, imines, diphenylethylene,
vinylanthracene, diaminocarbazole, pyrane, thiopyrane, polymethine,
merocyanine, oxinoid compounds chelated with imidazoles,
quinacridone, rubrene, stilbene derivatives and fluorescent dyes.
However, the examples of the above material are not limited to the
above compounds.
[0070] In particular, metal complexes of quinoline and stilbene
derivatives can be used in combination with the compounds
represented by general formulae [7] and [8] as the light emitting
material or the doping material in the light emitting layer.
[0071] It is essential that the content of the doping material in
the light emitting layer is greater than the content of the
compound represented by general formula [11] or [11']. It is
preferable that the content is 80 to 99.9% by weight.
[0072] As the hole injecting material, a compound which has the
ability to transfer holes, exhibits excellent effect of hole
injection from the anode and excellent effect of hole injection to
the light emitting layer or the light emitting material, prevents
transfer of excited components formed in the light emitting layer
into the electron injecting layer or the electron injecting
material and has an excellent ability to form a thin film is
preferable. Examples of such a compound include phthalocyanine
derivatives, naphthalocyanine derivatives, porphyrin derivatives,
oxaozole, oxadiazole, triazole, imidazole, imdazolone,
imdazolethione, pyrazoline, pyrazolone, tetrahydroimidazole,
oxazole, oxadiazole, hydrazone, acylhydrazone, polyarylalkanes,
stilbene, butadiene, benzidine-type triphenylamine, styrylamine
type triphenylamine, diamine type triphenylamine, derivatives of
these compounds and macromolecular compounds such as
polyvinylcarbazole, polysilane and conductive macromolecules.
However, examples of such a compound are not limited to the
compounds described above.
[0073] Among the hole injection materials which can be used in the
organic EL device of the present invention, more effective hole
injecting materials are aromatic tertiary amine derivatives and
phthalocyanine derivatives.
[0074] Examples of the aromatic tertiary amine derivative include
triphenylamine, tritolylamine, 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-phenylcyclohexane and oligomers
and polymers having a skeleton structure of these aromatic tertiary
amines. However, examples of the aromatic tertiary amine derivative
are not limited to the above compounds.
[0075] Examples of the phthalocyanine (Pc) derivative include
H.sub.2Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc,
ClGaPc, ClInPc, ClSnPc, Cl.sub.2SiPc, (HO)AlPc, (HO)GaPc, VOPc,
TiOPc, MoOPc, GaPc-O--GaPc and corresponding derivatives of
naphthalocyanine. However, examples of the derivatives of
phthalocyanine and naphthalocyanine are not limited to the above
compounds.
[0076] As the electron injecting material, a compound which has the
ability to transport electrons, exhibits excellent effect of
electron injection from the cathode and excellent effect of
electron injecting to the light emitting layer or the light
emitting material, prevents transfer of excited components formed
in the light emitting layer into the hole injecting layer or the
hole injecting material and has an excellent ability to form a thin
film is preferable. Examples of such a compound include fluorenone,
anthraquinodimethane, diphenoquinone, thiopyrane dioxide, oxazole,
oxadiazole, triazole, imidazole, peryleneteteracarboxylic acid,
fluorenylidenemethane, anthraquinodimethane, anthrone and
derivatives of these compounds. However, examples of such a
compound is not limited to the compounds described above. The
electron injecting property can be improved by adding an electron
accepting material to the hole injecting material or an electron
donating material to the electron injecting material.
[0077] In the organic EL device of the present invention, more
effective electron injecting materials are metal complex compounds
and five-membered derivatives containing nitrogen.
[0078] Examples of the metal complex compound include
8-hydroxyquinolinatolithium, bis(8-hydroxyquinolinato)zinc,
bis(8-hydroxyquinolinato)copper,
bis(8-hydroxyquinolinato)manganese,
tris(8-hydroxyquinolinato)aluminum,
tris(2-methyl-8-hydroxyquinolinato)-aluminum,
tris(8-hydroxyquinilinato)gallium,
bis(10-hydroxybenzo-[h]quinolinato)beryllium,
bis(10-hydroxybenzo[h]quinolinato)zinc,
bis(2-methyl-8-quinolinato)chlorogallium,
bis(2-methyl-8-quinolinato)(o-cresolato)gallium,
bis(2-methyl-8-quinolinato)(1-naphtholato)aluminum and
bis(2-methyl-8-quinolinato)(2-naphtholato)gallium. However,
examples of the metal complex compound are not limited to the above
compounds.
[0079] Preferable examples of the five-membered derivative
containing nitrogen include derivatives of oxazoles, thiazoles,
thiadiazoles and triazoles. Specific examples include
2,5-bis(1-phenyl)-1,3,4-oxazole, dimethylPOPOP,
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 and
1,4-bis[2-(5-phenyltriazolyl)]benzene. However, examples of the
five-membered derivative containing nitrogen are not limited to the
above compounds.
[0080] In the organic EL device of the present invention, at least
one of light emitting materials, doping materials, hole injecting
materials and electron injecting materials may be contained in the
same layer of the light emitting layer in addition to the compounds
represented by general formulae [1] and [3] to [8]. In order to
improve stability of the organic EL device of the present invention
with respect to the temperature, the humidity and the oxygen, a
protecting layer may be formed on the entire surface of the device
or the entire device may be protected with silicon oil or a
resin.
[0081] As the conductive material used as the anode of the organic
EL device, a material having a work function of 4 eV or greater is
suitable. Examples of such a material include carbon, aluminum,
vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum,
palladium, alloys of these metals, metal oxides used for ITO
substrates and NESA substrates such as tin oxide and indium oxide
and organic conductive resins such as polythiophene and polypyrrol.
As the conductive material used for the cathode, a material having
a work function smaller than 4 eV is suitable. Examples of such a
material include magnesium, calcium, tin, lead, titanium, yttrium,
lithium, ruthenium, manganese, aluminum and alloys of these metals.
However, examples of the materials used for the anode and the
cathode are not limited to the above examples. Typical examples of
the alloy include alloys of magnesium and silver, alloys of
magnesium and indium and alloys of lithium and aluminum. However,
examples of the alloy are not limited to these alloys. The
composition of the alloy is determined by the temperature of the
source of vapor deposition, the atmosphere and the degree of vacuum
and a suitable composition is selected. The anode and the cathode
may have a multi-layer structure having two or more layers, where
necessary;
[0082] In the organic EL device, it is preferable that at least one
face of the device is sufficiently transparent in the wave length
region of emitted light to achieve efficient light emission. It is
preferable that the substrate is also transparent. In the
preparation of the transparent electrode, the above conductive
material is used and vapor deposition or sputtering is conducted so
that the prescribed transparency is surly obtained. It is
preferable that the electrode disposed on the light emitting face
has a light transmittance of 10% or greater. The substrate is not
particularly limited as long as the substrate has mechanical
strength and strength at high temperatures and is transparent.
Glass substrates or transparent films of resins may be used.
Example of the transparent films of resins include films of
polyethylene, ethylene-vinyl acetate copolymers, ethylene-vinyl
alcohol copolymers, polypropylene, polystyrene, polymethyl
methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl
butyral, nylon, polyether ether ketones, polsulfones, polyether
sulfones, tetrafluoroethylene-perfluoroalkyl vinyl ether
copolymers, polyvinyl fluoride, tetrafluoroethylene-ethylene
copolymers, tetrafluoroethylene-hexafluoropropylene copolymers,
polychlorotrifluoroethylene, polyvinylidene fluoride, polyesters,
polycarbonates, polyurethanes, polyimides, polyether imides,
polyimides and polypropylene.
[0083] Each layer of the organic EL device of the present invention
can be produced suitably in accordance with a dry process of film
formation such as vacuum vapor deposition, sputtering and plasma
and ion plating or a wet process of film formation such as spin
coating, dipping and flow coating. The thickness of the film is not
particularly limited. However, it is necessary that the thickness
be set at a suitable value. When the thickness is greater than the
suitable value, a great voltage must be applied to obtain a
prescribed output of light and the efficiency deteriorates. When
the thickness is smaller than the suitable value, pin holes are
formed and a sufficient luminance cannot be obtained even when the
electric field is applied. In general, the suitable range of the
thickness is 5 nm to 10 .mu.m. A thickness in the range of 10 nm to
0.2 .mu.m is preferable.
[0084] When the device is produced in accordance with a wet
process, materials forming each layer are dissolved or dispersed in
a suitable solvent such as ethanol, chloroform, tetrahydrofuran and
dioxane and a film is formed from the solution or the suspension.
The solvent is not particularly limited. In any organic thin layer,
suitable resins and additives may be used to improve the property
to form a film and to prevent formation of pin holes. Examples of
the resin which can be used include insulating resins such as
polystyrene, polycarbonates, polyarylates, polyesters, polyamides,
polyurethanes, polysulfones, polymethyl methacrylate, polymethyl
acrylate and cellulose, copolymers derived from these resins,
photoconductive resins such as poly-N-vinylcarbazole and polysilane
and conductive resins such as polythiophene and polypyrrol.
Examples of the additive include antioxidants, ultraviolet light
absorbents and plasticizers.
[0085] As described above, by using the compounds of the present
invention for the light emitting layer of the organic EL device,
practically sufficient luminance can be obtained under application
of a low voltage. Therefore, the organic EL device exhibiting a
high efficiency of light emission and having a long life due to
suppressed degradation and excellent heat resistance can be
obtained.
[0086] The organic EL device of the present invention can be used
for a planar light emitting member such as a flat panel display of
wall televisions, a back light for copiers, printers and liquid
crystal displays, a light source of instruments, display panels and
a marker light.
[0087] The materials of the present invention can be used not only
for the organic EL devices but also in the field of electronic
photosensitive materials, opto-electric conversion devices, solar
batteries and image sensors.
[0088] Examples of the primary amine represented by general formula
[15] which is used in the process for producing a material for
organic EL devices of the present invention include primary
alkylamines such as methylamine, ethylamine, n-propylamine,
isopropylamine, n-butylamine, isobutylamine, sec-butylamine,
tert-butylamine, n-amylamine, isoamylamine, tert-amylamine,
cyclohexylamine, n-hexylamine, heptylamine, 2-aminoheptane,
3-aminoheptane, octylamine, nonylamine, decylamine, undecylamine,
dodecylamine, tridecylamine, 1-tetradecylamine, pentadecylamine,
1-hexadecylamine and octadecylamine; primary alkyldiamines such as
ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane and
1,4-diaminobutane; arylamines such as aniline, o-fluoroaniline,
m-fluoroaniline, p-fluoroaniline, o-toluidine, m-toluidine,
p-toluidine, o-anisidine, m-anisidine, p-anisidine,
1-naphthylamine, 2-naphthylamine, 1-aminoanthracene,
2-aminoanthracene, 2-aminobiphenyl, 4-aminobiphenyl,
9-aminophenanthrene, 2-trifluoromethyltoluidine,
3-trifluoromethyltoluidine and 4-trifluoromethyltoluidine;
aryldiamines such as o-phenylenediamine, m-phenylenediamine,
p-phenylenediamine, fluorenediamine and 1,8-naphthalenediamine; and
the following compounds: ##STR56##
[0089] Examples of the secondary amine represented by general
formula [15] include the following compounds: ##STR57##
##STR58##
[0090] The aryl halide represented by general formula [16] is not
particularly limited. The group represented by Ar is, in general,
an alkyl group having 1 to 18 carbon atoms or a substituted or
unsubstituted aryl group having 6 to 22 carbon atoms. The aromatic
ring may have substituents. In the present invention, the aryl
group include hydrocarbon groups having condensed rings.
[0091] Examples of the aryl halide include aryl bromides such as
bromobenzene, o-bromoanisole, m-bromoanisole, p-bromoanisole,
o-bromotoluene, m-bromotoluene, p-bromotoluene, o-bromophenol,
m-bromophenol, p-bromophenol, 2-bromobenzotrifluoride,
3-bromobenzotrifluoride, 4-bromobenzenetrifluoride,
1-bromo-2,4-dimethoxybenzene, 1-bromo-2,5-dimethoxybenzene,
2-bromophenetyl alcohol, 3-bromophenetyl alcohol, 4-bromophenetyl
alcohol, 5-bromo-1,2,4-trimethylbenzene, 2-bromo-m-xylene,
2-bromo-p-xylene, 3-bromo-o-xylene, 4-bromo-o-xylene,
4-bromo-m-xylene, 5-bromo-m-xylene,
1-bromo-3-(trifluoromethoxy)benzene,
1-bromo-4-(trifluoromethoxy)benzene, 2-bromobiphenyl,
3-bromobiphenyl, 4-bromobiphenyl,
4-bromo-1,2-(methylenedioxy)benzene, 1-bromonaphthalene,
2-bromonaphthalene, 1-bromo-2-methylnaphthalene and
1-bromo-4-methylnaphthalene; aryl chlorides such as chlorobenzene,
o-chloroanisole, m-chloroanisole, p-chloroanisole, o-chlorotoluene,
m-chlorotoluene, p-chlorotoluene, o-chlorophenol, m-chlorophenol,
p-chlorophenol, 2-chlorobenzotrifluoride, 3-chlorobenzotrifluoride,
4-chlorobenzenetrifluoride, 1-chloro-2,4-dimethoxybenzene,
1-chloro-2,5-dimethoxybenzene, 2-chlorophenetyl alcohol,
3-chlorophenetyl alcohol, 4-chlorophenetyl alcohol,
5-chloro-1,2,4-trimethylbenzene, 2-chloro-m-xylene,
2-chloro-p-xylene, 3-chloro-o-xylene, 4-chloro-o-xylene,
4-chloro-m-xylene, 5-chloro-m-xylene,
1-chloro-3-(trifluoromethoxy)benzene,
1-chloro-4-(trifluoromethoxy)benzene, 2-chlorobiphenyl,
3-chlorobiphenyl, 4-chlorobiphenyl, 1-chloronaphthalene,
2-chloronaphthalene, 1-chloro-2-methylnaphthalene and
1-chloro-4-methylnaphthalene; aryl iodides such as iodobenzene,
o-iodoanisole, m-iodoanisole, p-iodoanisole, o-iodotoluene,
m-iodotoluene, p-iodotoluene, o-iodophenol, m-iodophenol,
p-iodophenol, 2-iodobenzotrifluoride, 3-iodobenzotrifluoride,
4-iodobenzenetrifluoride, 1-iodo-2,4-dimethoxybenzene,
1-iodo-2,5-dimethoxybenzene, 2-iodophenetyl alcohol, 3-iodophenetyl
alcohol, 4-iodophenetyl alcohol, 5-iodo-1,2,4-trimethylbenzene,
2-iodo-m-xylene, 2-iodo-p-xylene, 3-iodo-o-xylene, 4-iodo-o-xylene,
4-iodo-m-xylene, 5-iodo-m-xylene,
1-iodo-3-(trifluoromethoxy)benzene,
1-iodo-4-(trifluoromethoxy)benzene, 2-iodobiphenyl, 3-iodobiphenyl,
4-iodobiphenyl, 1-iodonaphthalene, 2-iodonaphthalene,
1-iodo-2-methylnaphthalene and 1-iodo-4-methylnaphthalene; aryl
fluorides such as fluorobenzene, o-fluoroanisole, m-fluoroanisole,
p-fluoroanisole, o-fluorotoluene, m-fluorotoluene, p-fluorotoluene,
o-fluorophenol, m-fluorophenol, p-fluorophenol,
2-fluorobenzotrifluoride, 3-fluorobenzotrifluoride,
4-fluorobenzenetrifluoride, 1-fluoro-2,4-dimethoxybenzene,
1-fluoro-2,5-dimethoxybenzene, 2-fluorophenetyl alcohol,
3-fluorophenetyl alcohol, 4-fluorophenetyl alcohol,
5-fluoro-1,2,4-trimethylbenzene, 2-fluoro-m-xylene,
2-fluoro-p-xylene, 3-fluoro-o-xylene, 4-fluoro-o-xylene,
4-fluoro-m-xylene, 5-fluoro-m-xylene,
1-fluoro-3-(trifluoromethoxy)benzene,
1-fluoro-4-(trifluoromethoxy)benzene, 2-fluorobiphenyl,
3-fluorobiphenyl, 4-fluorobiphenyl,
4-fluoro-1,2-(methylenedioxy)benzene, 1-fluoronaphthalene,
2-fluoronaphthalene, 1-fluoro-2-methylnaphthalene and
1-fluoro-4-methylnaphthalene; and the following compounds:
##STR59## ##STR60##
[0092] Aryl halides having 2 or more halogen atoms and preferably 2
or 3 halogen atoms can also be used as long as the object of the
present invention is not adversely affected. Examples of the aryl
halide having 2 or more halogen atoms include 1,2-dibromobenzene,
1,3-dibromobenzene, 1,4-dibromobenzene, 9,10-dibromoanthracene,
9,10-dichloroanthracene, 4,4'-dibromobiphenyl,
4,4'-dichlorobiphenyl, 4,4'-diiodobiphenyl,
1-bromo-2-fluorobenzene, 1-bromo-3-fluorobenzene,
1-bromo-4-fluorobenzene, 2-bromochlorobenzene,
3-bromochlorobenzene, 4-bromochlorobenzene,
2-bromo-5-chlorotoluene, 3-bromo-4-chlorobenzotrifluoride,
5-bromo-2-chlorobenzotrifluoride, 1-bromo-2,3-dichlorobenzene,
1-bromo-2,6-dichlorobenzene, 1-bromo-3,5-dichlorobenzene,
2-bromo-4-fluorotoluene, 2-bromo-5-fluorotoluene,
3-bromo-4-fluorotoluene, 4-bromo-2-fluorotoluene,
4-bromo-3-fluorotoluene, tris(4-bromophenyl)amine,
1,3,5-tribromobenzene and the following compounds: ##STR61##
##STR62##
[0093] In the process for producing materials for organic EL
devices of the present invention, the method of addition of the
aryl halide is not particularly limited. For example, two different
types of aryl halides may be mixed with a primary amine before
starting the reaction and the reaction may be conducted using the
obtained mixture. Alternatively, a primary amine may be reacted
with one of two types of aryl halides. Then, the obtained secondary
amine may be added to the other aryl halide and the reaction is
conducted. The latter method in which different aryl halides are
added successively is preferable because a tertiary amine can be
produced more selectively.
[0094] The amount of the added aryl halide is not particularly
limited. When the two types of aryl halides are added to the
primary amine simultaneously, it is suitable that the amount of the
aryl halide is in the range of 0.5 to 10 moles per 1 mole of the
primary amine. From the standpoint of economy and easier treatments
after the reaction such as separation of the unreacted aryl halide,
it is preferable that the amount of the aryl halide is in the range
of 0.7 to 5 moles per 1 mole of the primary amine. When the two
types of aryl halides are added successively to the primary amine,
the aryl halide which is added first is added to the reaction
system in an amount in the range of 0.5 to 1.5 moles per 1 mole of
the amino group in the primary amine. From the standpoint of
improving the selectivity of the tertiary amine of the object
compound, it is preferable that the above aryl halide is added to
the reaction system in an amount of 0.9 to 1.1 mole per 1 mole of
the amino group in the primary amine.
[0095] The arylthalide which is added after preparation of the
secondary amine is added in an amount of 0.1 to 10 mole per 1 mole
of the amino group in the primary amine used as the starting
material. To prevent complicated operations in separation of the
unreacted aryl halide and the unreacted secondary amine after the
reaction, it is preferable that the aryl halide is added in an
amount of 0.9 to 5 mole per 1 mole of the amino group in the
primary amine used as the starting material.
[0096] The palladium compound used as the catalyst component in the
present invention is not particularly limited as long as it is a
compound of palladium. Examples of the palladium compound include
compounds of tetravalent palladium such as sodium
hexachloropalladate(IV) tetrahydrate and potassium
hexachloropalladate(IV); compounds of divalent palladium such as
palladium(II) chloride, palladium(II) bromide, palladium(II)
acetate, palladium acetylacetonate(II),
dichlorobis-(benzonitrile)palladium(II),
dichlorobis(acetonitrile)palladium(II),
dichloro(bis(diphenylphosphino)ethane)palladium(II),
dichlorobis-(triphenylphosphine)palladium(II),
dichlorotetraamminepalladium(II),
dichloro(cycloocta-1,5-diene)palladium(II) and palladium
trifluoroacetate(II); and compounds of zero-valent palladium such
as tris(dibenzylideneacetone)dipalladium(0) (Pd.sub.2(dba).sub.3),
chloroform complex of tris(dibenzylideneacetone)dipalladium(0),
tetrakis(triphenylphosphine)palladium(0) and
bis(bis(diphenylphosphino)ethane-palladium(0). In the process of
the present invention, the amount of the palladium compound is not
particularly limited. The amount of the palladium compound is
0.00001 to 20.0% by mole as the amount of palladium per 1 mol of
the primary amine. The tertiary amine can be synthesized with a
high selectivity when the amount of the palladium compound is in
the above range. Since the palladium compound is expensive, it is
preferable that the amount of the palladium compound is 0.001 to
5.0 mole as the amount of palladium per 1 mole of the primary
amine.
[0097] In the process of the present invention, the
trialkylphosphine compound used as the catalyst component is not
particularly limited. Examples of the trialkylphosphine compound
include triethylphosphine, tricyclohexylphosphine,
triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine,
tri-sec-butylphosphine and tri-tert-butylphosphine. Among these
compounds, tri-tert-butylphosphine is preferable because of the
high reaction activity. The triarylphosphine compound is not
particularly limited. Examples of the triarylphosphine include
triphenylphosphine, benzyldiphenylphosphine, tri-o-toluylphosphine,
tri-m-toluylphosphine and tri-p-toluylphosphine. Among these
compounds, triphenylphosphine and tri-o-toluylphosphine are
preferable. The diphosphine compound is not particularly limited.
Examples of the diphosphine compound include
bis(dimethylphosphino)methane, bis(dimethylphosphino)ethane,
bis(dicyclohexylphosphino)methane,
bis(dicyclohexylphosphino)ethane, bis(diphenylphosphino)ethane,
1,3-bis(diphenylphosphino)propane,
1,4-bis(diphenylphosphino)butane, bis(diphenylphosphino)ferrocene,
(R)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl((R)-BINAP),
(S)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl-((S)-BINAP),
2,2'-bis(diphenylphosphino)-1,1'-bisnaphthyl((.+-.)-BINAP),
2S,3S-bis(diphenylphosphino)butane((S,S)-CHIRAPHOS),
2R,3R-bis(diphenylphosphino)butane ((R,R)-CHIRAPHOS),
2,3-bis(diphenylphosphino)butane(.+-.)-CHIRAPHOS),
(R)-2,2'-bis(di-p-toluylphosphino)-1,1-binaphthyl((R)Tol-BINAP),
(S)-2,2'-bis(di-p-toluylphosphino)-1,1'-binaphthyl((S)-Tol-BINAP),
2,2'-bis(di-p-toluylphosphino)-1,1'-bisnaphthyl((.+-.)-Tol-BINAP),
4R,5R-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxorane((R,R)-DIOP)-
,
4S,5S-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dioxorane(S,S)-DIOP)-
,
4,5-bis(diphenylphosphinomethyl)-2,2-dimethyl-1,3-dixorane((.+-.)-DIOP),
N,N'-dimethyl-(S)-1-[(R)-1',2-bis(diphenylphosphino)ferrocenyl]ethylamine-
((S),(R)-BPPFA),
N,N'-dimethyl-(R)-1-[(S)-1',2-bis(diphenylphosphino)ferrocenyl]-ethylamin-
e((R),(S)-BPPFA) and
N,N'-dimethyl-1-[1',2-bis(diphenylphosphino)ferrocenyl]ethylamine((.+-.)--
BPPFA). Among these compounds, bis(diphenylphosphino)ethane,
1,3-bis(diphenylphosphino)propane, bis(diphenylphosphino)ferrocene
and BINAPs are preferable. BINAPs may be either optically active
compounds or racemic compounds.
[0098] The amounts of the trialkylphosphine compound, the
triphenylphosphine compound and the diphosphine compound are 0.01
to 10,000 mole per 1 mole of the palladium compound. As long as the
amounts are in this range, the selectivity of the arylamine does
not change. However, it is preferable that the amount is 0.1 to 10
mole per 1 mol of the palladium compound since the phosphine
compounds are expensive.
[0099] In the process of the present invention, the palladium
compound and the phosphine compound are the essential components of
the catalyst. The combination of these components is added to the
reaction system as the catalyst. As the method of addition of the
components, the two components may be added to the reaction system
separately or in the form of a complex which is prepared in
advance.
[0100] The base which can be used in the present reaction is not
particularly limited and can be selected from inorganic bases such
as sodium carbonate and potassium carbonate and alkali metal
alkoxides and organic bases such as tertiary amines. Preferable
examples of the base include alkali metal alkoxides such as sodium
mothoxide, sodium ethoxide, potassium methoxide, potassium
ethoxide, lithium tert-butoxide, sodium tert-butoxide, potassium
tert-butoxide and cesium carbonate (Cs.sub.2CO.sub.3). The base may
be added into the reaction field without any treatment.
Alternatively, the base may be prepared from an alkali metal, a
hydrogenated alkali metal or a alkali metal hydroxide and an
alcohol at the place of reaction and used in the reaction
field.
[0101] The amount of the base is not particularly limited. It is
preferable that the amount is 0.5 mole or more per 1 mole of the
halogen atom in the two different types of aryl halides which are
added to the reaction system. When the amount of the base is less
than 0.5 mol, the activity of the reaction decreases and the yield
of the arylamine decreases. Therefore, such an amount is not
preferable. When the base is added in a great excess amount, the
yield of the arylamine does not change and, on the other hand,
treatments after the reaction become complicated. Therefore, it is
more preferable that the amount is 1.0 mole or more and less than 5
mole per 1 mole of the halogen atom.
[0102] The reaction in the process of the present invention is
conducted, in general, in the presence of an inert solvent. The
solvent is not particularly limited as long as the solvent does not
adversely affect the reaction much. Examples of the solvent include
aromatic hydrocarbon solvents such as benzene, toluene and xylene,
ether solvents such as diethyl ether, tetrahydrofuran and dioxane,
acetonitrile, dimethylformamide, dimethylsulfoxide and
hexamethylphosphotriamide. Aromatic hydrocarbon solvents such as
benzene, toluene and xylene are preferable.
[0103] It is preferable that the process of the present invention
is conducted under the ordinary pressure in an atmosphere of an
inert gas such as nitrogen and argon. The process can be conducted
also under an added pressure.
[0104] In the process of the present invention, the temperature of
the reaction can be selected in the range of 20 to 300.degree. C.
and preferably in the range of 50 to 200.degree. C. The time of the
reaction can be selected in the range of several minutes to 72
hours.
[0105] The process of the present invention in which the arylamine
compound is obtained in the presence of the catalyst comprising the
phosphine compound and the palladium compound and the base is
specifically described in Synthesis Examples 12, 13, 14, 17 and
20.
[0106] The present invention will be described more specifically
with reference to examples in the following. However, the present
invention is not limited to the examples.
SYNTHESIS EXAMPLE 1 (COMPOUND (2))
[0107] Synthesis of Intermediate Compound A
[0108] In a 200 ml round bottom flask, 0.38 g (2.04 mmole) of
4-bromobenzaldehyde and 0.98 g (4.29 mmole) of ethyl
benzylphosphonate were dissolved in 40 ml of dimethylsulfoxide. To
this was added 0.5 g (4.49 mmole) of potassium t-butoxide in small
portions at the room temperature and the resulting mixture was
stirred for 18 hours. The reaction mixture was poured into 500 ml
of water, solid was filtered to give yellow solid (0.5 g).
[0109] In a 100 ml round bottom flask, the crystals obtained above,
2.0 g (12.0 mmole) of potassium iodide and 1.14 g (6.0 mmole) of
copper iodide were dissolved in 10 ml of hexamethylphosphoramide
and the resulting mixture was stirred under heating at 150.degree.
C. for 6 hours. After the reaction was completed, 10 ml of a 1 N
aqueous hydrochloric acid was added to the reaction mixture and the
organic layer was extracted with toluene. After the extract was
concentrated, the reaction product was purified by recrystallizing
from a mixture of diethyl ether and methanol and 0.28 g (the yield:
45%) of the following Intermediate Compound A was obtained:
##STR63##
[0110] Synthesis of Intermediate Compound B
[0111] In a 50 ml round bottom flask, 3 g (17.4 mmole) of
p-bromoaniline was suspended in 10 ml of a 6 N aqueous hydrochloric
acid and cooled. To the cooled suspension, a solution prepared by
dissolving 1.25 g (18.1 mmole) of sodium sulfite in 5.3 ml of water
was slowly added dropwise at an inner temperature of 4.degree. C.
The resulting mixture was stirred at the same temperature for 1
hour and an aqueous solution of a diazonium compound was
obtained.
[0112] Separately, in a 100 ml round bottom flask, 0.3 g (1.7
mmole) of anthracene was dissolved in 5 ml of acetone. To this was
added a solution prepared by dissolving 0.46 g of copper(II)
chloride dihydrate in 5.7 ml of water and the mixture was cooled to
4.degree. C. To the cooled mixture, the aqueous solution of a
diazonium compound obtained above was added at the same temperature
and the resulting mixture was stirred for over night at the room
temperature. After the reaction was completed, precipitated
crystals were filtered, washed with methanol and dried and 0.2 g
(the yield: 24%) of the following Intermediate Compound B was
obtained: ##STR64##
[0113] Synthesis of Compound (2)
[0114] In a 100 ml round bottom flask, 0.018 g (0.2 mmole) of
aniline was dissolved in 5 ml of methylene chloride. To this was
added 0.05 g (0.5 mmole) of acetic anhydride and the resulting
mixture was stirred at the room temperature for 1 hour. Then, the
reaction solvent was removed by distillation and an oily compound
was obtained. To the oily compound, 0.56 g (1.8 mmole) of
Intermediate Compound A, 5 g of potassium carbonate, 0.3 g of
copper powder and 20 ml of nitrobenzene were added and the
resulting mixture was stirred at 210.degree. C. for 2 days. Then,
the solvent was removed by distillation and 10 ml of diethylene
glycol and a solution prepared by dissolving 3 g of potassium
hydroxide into 10 ml of water were added. The resulting mixture was
stirred at 110.degree. C. for one night. After the reaction was
completed, a mixture of ethyl acetate and water was added to the
reaction mixture and the organic layer was separated. After the
solvent was removed by distillation, crude crystals were
obtained.
[0115] Subsequently, into a 100 ml round bottom flask, the crude
crystal obtained above, 0.05 g (0.1 mmole) of Intermediate Compound
B, 5 g of potassium carbonate, 0.3 g of copper powder and 20 ml of
nitrobenzene were placed and the mixture was stirred under heating
at 220.degree. C. for 2 days. After the reaction was completed,
precipitated crystals were separated by filtration, washed with
methanol, dried and purified in accordance with the column
chromatography (silica gel, hexane/toluene=1/1) and 0.017 g of
yellow powder was obtained. The powder was identified to be
Compound (2) by the measurements in accordance with NMR, IR and
FD-MS (the field desorption mass spectrometry) (the yield:
20%).
SYNTHESIS EXAMPLE 2 (COMPOUND (9))
[0116] Synthesis of Intermediate Compound C
[0117] In a 200 ml round bottom flask, 51.2 g (0.3 mole) of
diphenylamine, 71.4 g (0.3 mole) of 1,4-dibromobenzene, 34.6 g
(0.36 mole) of potassium t-butoxide, 4.2 g (5.9 mmole) of
PdCl.sub.2(PPh.sub.3).sub.2 and 1.2 liter of xylene were mixed
together and the obtained mixture was stirred at 130.degree. C. for
one night.
[0118] After the reaction was completed, the organic layer was
concentrated and about 100 g of brown crystals were obtained. The
crystals were purified in accordance with the column chromatography
(silica gel, hexane/toluene=10/1) and 28 g (the yield: 29%) of the
following Intermediate Compound C was obtained: ##STR65##
[0119] Synthesis of Compound (9)
[0120] In a 100 ml round bottom flask, 0.48 g (1 mmole) of
Intermediate Compound B was dissolved in 10 ml of diethyl ether and
the mixture was cooled to -78.degree. C. To the cooled mixture, 2
ml (1.5 M, 3 mmole) of n-butyllithium was added and the resulting
mixture was stirred for 1 hour. Then, a solution prepared by
dissolving 0.3 g (3 mmole) of trimethyl borate in 5 ml of diethyl
ether was added dropwise to the mixture. After the addition was
completed, the resulting mixture was stirred at -78.degree. C. for
1 hour. Then, 10 ml of a 1 N aqueous hydrochloric acid was added at
the room temperature. After the organic layer was separated, the
solvent was removed by distillation and crude crystals were
obtained.
[0121] In a 100 ml round bottom flask, the crude crystals obtained
above, 0.97 g (3 mmole) of Intermediate Compound C, 12 mg of
Pd(PPh.sub.3).sub.4 and 0.32 g (1.5 mmole) of potassium phosphate
were dissolved in 10 ml of dimethylformamide and the resulting
mixture was stirred at 100.degree. C. for 4 hours. After the
organic layer was separated, the solvent was removed by
distillation and crude crystals were obtained. The crude crystals
were purified by the column chromatography (silica gel,
benzene/ethyl acetate=50/1) to give 0.13 g of yellow powder. The
powder was identified to be Compound (9) by the measurements in
accordance with NMR, IR and FD-MS (the yield: 14%).
SYNTHESIS EXAMPLE 3 (COMPOUND (18))
[0122] Synthesis of Intermediate Compound D
[0123] A Grignard reagent was prepared by adding magnesium and
diethyl ether to 0.48 g (2.0 mmol) of 1,4-dibromobenzene.
Separately, in a 100 ml round bottom flask, 5.7 g (20.0 mmole) of
1,4-dibromonaphthalene and 10 mg of NiCl.sub.2(dppp) were dissolved
in 20 ml of diethyl ether and the resulting mixture was cooled in
an ice bath. To the cooled mixture, the Grignard reagent prepared
above was added and the obtained mixture was stirred under
refluxing for 6 hours. After the reaction was completed, 10 ml of a
1 N aqueous hydrochloric acid was added. After the organic layer
was separated, the solvent was removed by distillation and 0.30
(the yield: 30%) of the following Intermediate Compound D was
obtained: ##STR66##
[0124] Synthesis of Compound (18)
[0125] In a 100 ml round bottom flask, 0.09 g (1.0 mmole) of
aniline and 0.25 g (2.5 mmole) of acetic anhydride were dissolved
into 5 ml of methylene chloride. The resulting mixture was stirred
at the room temperature for 1 hour. Then, the solvent was removed
by distillation and an oily compound was obtained. To this was
added 0.4 g (4.5 mmole) of Intermediate Compound A, 5 g of
potassium carbonate, 0.3 g of copper powder and 20 ml of
nitrobenzene and the resulting mixture was stirred under heating at
210.degree. C. for 2 days. Then, the solvent was removed by
distillation and 10 ml of diethylene glycol and a solution prepared
by dissolving 3 g of potassium hydroxide into 10 ml of water were
added to the residue. The resulting mixture was stirred at
110.degree. C. for one night. After the reaction was completed, a
mixture of ethyl acetate and water was added to the reaction
mixture. After the organic layer was separated, the solvent was
removed and crude crystals were obtained.
[0126] Subsequently, into a 100 ml round bottom flask, the above
crude crystals, 0.5 g (1.0 mmole) of Intermediate Compound D, 5 g
of potassium carbonate and 0.3 g of copper powder were dissolved in
20 ml of nitrobenzene and the resulting mixture was stirred under
heating at 220.degree. C. for 2 days. After the reaction was
completed, precipitated crystals were filtered, washed with
methanol, dried and purified by the column chromatography (silica
gel, hexane/toluene=1/1) to give 0.1 g of yellow powder. The powder
was identified to be Compound (18) by the measurements in
accordance with NMR, IR and FD-MS (the yield: 10%).
EXAMPLE 1
[0127] A cleaned glass plate having an ITO electrode was coated
with a composition which contained Compound (2) obtained above as
the light emitting material, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole
and a polycarbonate resin (manufactured by TEIJIN KASEI Co., Ltd.;
PANLITE K-1300) in amounts such that the ratio by weight was 5:3:2
and was dissolved in tetrahydrofuran in accordance with the spin
coating and a light emitting layer having a thickness of 100 nm was
obtained. On the obtained light emitting layer, an electrode having
a thickness of 150 nm was formed with an alloy prepared by mixing
aluminum and lithium in amounts such that the content of lithium
was 3% by weight and an organic EL device was obtained. The organic
EL device exhibited a luminance of emitted light of 200
(cd/m.sup.2), the maximum luminance of 14,000 (cd/m.sup.2) and an
efficiency of light emission of 2.1 (lm/W) under application of a
direct current voltage of 5 V.
EXAMPLE 2
[0128] On a cleaned glass plate having an ITO electrode, Compound
(9) obtained above was vacuum vapor deposited as the light emitting
material and a light emitting layer having a thickness of 100 nm
was formed. On the layer formed above, an electrode having a
thickness of 100 nm was formed with an alloy prepared by mixing
aluminum and lithium in amounts such that the content of lithium
was 3% by weight and an organic EL device was obtained. The light
emitting layer was formed by vapor deposition under a vacuum of
10.sup.-6 Torr while the temperature of the substrate was kept at
the room temperature. The organic EL device exhibited a luminance
of emitted light of about 110 (cd/m.sup.2), the maximum luminance
of 20,000 (cd/m.sup.2) and an efficiency of light emission of 2.1
(lm/W) under application of a direct current voltage of 5 V.
EXAMPLE 3
[0129] On a cleaned glass plate having an ITO electrode, Compound
(2) obtained above was vacuum vapor deposited as the light emitting
material and a light emitting layer having a thickness of 50 nm was
formed. Then, an electron injecting layer having a thickness of 10
nm was formed by vapor deposition of the following compound (Alq):
##STR67## On the layer formed above, an electrode having a
thickness of 100 nm was formed with an alloy prepared by mixing
aluminum and lithium in amounts such that the content of lithium
was 3% by weight and an organic EL device was obtained. The light
emitting layer and the electron injecting layer were formed by
vapor deposition under a vacuum of 10.sup.-6 Torr while the
temperature of the substrate was kept at the room temperature. The
organic EL device emitted bluish green light with a luminance of
emitted light of about 600 (cd/m.sup.2), the maximum luminance of
30,000 (cd/m.sup.2) and an efficiency of light emission of 3.0
(lm/W) under application of a direct current voltage of 5 V. When
the organic EL device was driven by a constant electric current at
an initial luminance of emitted light of 600 (cd/m.sup.2), the half
life time was as long as 2,000 hours.
EXAMPLES 4 TO 16
[0130] On a cleaned glass plate having an ITO electrode, the light
emitting material shown in Table 1 was vapor deposited and a light
emitting layer having a thickness of 80 nm was obtained. Then, the
compound (Alq) described above was vacuum vapor deposited as the
electron injecting material and an electron injecting layer having
a thickness of 20 nm was formed. On the layer formed above, an
electrode having a thickness of 150 nm was formed with an alloy
prepared by mixing aluminum and lithium in amounts such that the
content of lithium was 3% by weight. Organic EL devices were
obtained in this manner. The above layers were formed by vapor
deposition under a vacuum of 10.sup.-6 Torr while the temperature
of the substrate was kept at the room temperature. The light
emitting properties of the obtained devices are shown in Table 1.
The organic EL devices in these Examples all showed excellent
luminances such as the maximum luminance of 10,000 (cd/m.sup.2) or
greater. TABLE-US-00001 TABLE 1 Efficiency of Example Type of light
emitting light emission Half life time No. material (lm/W) (hour) 4
(3) 2.8 3200 5 (4) 2.4 2600 6 (5) 3.0 3200 7 (6) 1.2 1200 8 (9) 2.8
2800 9 (10) 1.7 1700 10 (13) 1.0 1400 11 (14) 2.1 2700 12 (15) 2.9
4200 13 (18) 1.6 1300 14 (20) 2.6 1800 15 (26) 3.1 4000 16 (27) 1.4
2100
EXAMPLE 17
[0131] On a cleaned glass plate having an ITO electrode, the
following compound (TPD74): ##STR68## was vacuum vapor deposited as
the hole injecting material and a film having a thickness of 60 nm
was formed. Then, the following compound (NPD): ##STR69## was
vacuum vapor deposited on the film formed above as the hole
transporting material and a film having a thickness of 20 nm was
formed. Then, 4,4'-bis(2,2-diphenylvinyl)biphenyl (DPVBi) and
Compound (3) obtained above were vapor deposited simultaneously and
a layer having a content of Compound (3) of 5% by weight and the
thickness of 40 nm was formed. Compound (3) works as the
fluorescent dopant. Subsequently, the compound (Alq) was vapor
deposited as the electron injecting material and a layer having a
thickness of 20 nm was formed. Then, LiF was vapor deposited and a
layer having a thickness of 0.5 nm was formed. An electrode was
formed on the above layers by vapor deposition of aluminum and a
layer having a thickness of 100 nm was formed. Thus, an organic EL
was obtained. The above layers were formed by vapor deposition
under a vacuum of 10.sup.-6 Torr while the temperature of the
substrate was kept at the room temperature. The organic EL device
exhibited a luminance of emitted light as high as about 750
(cd/m.sup.2) under application of a direct current voltage of 5 V.
When the organic EL device was driven by a constant electric
current at an initial luminance of emitted light of 400
(cd/m.sup.2), the half life time was as long as 3,000 hours.
COMPARATIVE EXAMPLE 1
[0132] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 1 except that the
following Compound of Comparative Example 1: ##STR70##
[0133] (Compound of Comparative Example 1)
[0134] was used as the light emitting material. The obtained
organic EL device exhibited a luminance of emitted light of 60
(cd/m.sup.2) and an efficiency of light emission of 0.34 (lm/W)
under application of a direct current voltage of 5 V. Sufficient
properties could not be obtained.
COMPARATIVE EXAMPLE 2
[0135] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 3 except that the
following Compound of Comparative Example 2: ##STR71##
[0136] (Compound of Comparative Example 2)
[0137] was used as the light emitting material. The obtained
organic EL device exhibited a luminance of emitted light of 200
(cd/m.sup.2) and an efficiency of light emission of 1.2 (lm/W)
under application of a direct current voltage of 5 V. However, when
the organic EL device was driven by a constant electric current at
an initial luminance of emitted light of 400 (cd/m.sup.2), the half
life time was as short as 600 hours.
Test of Heat Resistance
[0138] The organic EL devices prepared in Examples 2 and 3 and
Comparative Examples 1 and 2, which had been used for the
measurement of luminance of emitted light, were placed in a chamber
kept at the constant temperature of 100.degree. C. After 500 hours,
luminance of light emission was measured again. The values of
luminance before and after the devices were kept in the chamber
were compared and the retention of luminance was calculated.
[0139] The retentions of luminance of the organic EL devices
prepared in Examples 2 and 3 and Comparative Examples 1 and 2 thus
obtained were 85%, 90%, 25% and 30%, respectively. As shown by this
result, the compounds used as the light emitting material in
Comparative Examples 1 and 2 could not retain luminance because the
compounds had glass transition temperatures lower than 100.degree.
C. In contrast, the compounds used as the light emitting material
in Examples 2 and 3 exhibited excellent heat resistance and could
retain luminance for a long time because the compounds had glass
transition temperatures higher than 110.degree. C.
SYNTHESIS EXAMPLE 4 (COMPOUND (30))
[0140] Synthesis of Intermediate Compound E
(6,12-diiodochrysene)
[0141] In a 300 ml round bottom flask, 5 g (22 mmole) of chrysene
was dissolved in 100 ml of carbon tetrachloride. To this was added
16 g (64 mmole) of iodine dissolved in 100 ml of carbon
tetrachloride dropwise at the room temperature. The resulting
mixture was stirred under heating for 5 hours, precipitated
crystals were separated by filtration and the crystals were washed
with 100 ml of carbon tetrachloride. The crude crystals were
recrystallized from 200 ml of toluene and Intermediate Compound E
was obtained (the yield: 35%).
[0142] Synthesis of Compound (30)
[0143] In a 100 ml two-necked flask, 2 g (10 mmole) of
4-aminostilbene was dissolved in 20 ml of methylene chloride. To
this was added 2.5 g (25 mmole) of acetic anhydride. The resulting
mixture was stirred at the room temperature for 1-hour. Then, the
reaction solvent was removed by distillation and an oily compound
was obtained. In a 300 ml two-necked flask, 4.1 g (20 mmole) of
iodobenzene, 3 g (30 mmole) of potassium carbonate, 0.06 g (1
mmole) of copper powder and 100 ml of nitrobenzene were added to
the obtained oily compound and the obtained mixture was stirred
under heating at 220.degree. C. for 2 days. Then, the solvent was
removed by distillation and 10 ml of diethylene glycol and a
solution prepared by dissolving 30 g of potassium hydroxide into
100 ml of water were added to the residue. The reaction was allowed
to proceed at 110.degree. C. for one night. After the reaction was
completed, a mixture of ethyl acetate and water was added to the
reaction mixture. After the organic layer was separated, the
solvent was removed by distillation and crude crystals were
obtained.
[0144] Subsequently, in a 300 ml two-necked flask, the above crude
crystals, 2.4 g (5 mmole) of Intermediate Compound E, 3 g (20
mmole) of potassium carbonate and 0.06 g (1 mmole) of copper powder
were dissolved in 100 ml of nitrobenzene and the resulting mixture
was stirred under heating at 230.degree. C. for 2 days. After the
reaction was completed, precipitated crystals were separated by
filtration, washed with methanol, dried and purified in accordance
with the column chromatography (silica gel, hexane/toluene=1/1) and
1.0 g of yellow powder was obtained. The powder was identified to
be Compound (30) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 25%).
SYNTHESIS EXAMPLE 5 (COMPOUND (36))
[0145] Synthesis of Compound (36)
[0146] In a 100 ml round bottom flask, 3.4 g (20 mmole) of
diphenylamine, 4.8 g (10 mmole) of Intermediate Compound E, 3 g (30
mmole) of potassium carbonate and 0.06 g (1 mmole) of copper powder
were dissolved in 100 ml of nitrobenzene and the resulting mixture
was stirred under heating at 210.degree. C. for 2 days. After the
reaction was completed, precipitated crystals were separated by
filtration, washed with methanol, dried and purified in accordance
with the column chromatography (silica gel, hexane/toluene=1/1) and
2.8 g of yellow powder was obtained. The powder was identified to
be Compound (36) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 50%).
SYNTHESIS EXAMPLE 6 (COMPOUND (38))
[0147] Synthesis of Compound (38)
[0148] In a 100 ml four-necked flask, 1.0 g (41 mmole) of
magnesium, 1 ml of tetrahydrofuran and a small piece of iodine were
placed under an argon stream. To this mixture, 9.7 g (30 mmole) of
4-bromotriphenylamine dissolved in 100 ml of tetrahydrofuran was
slowly added dropwise at the room temperature. After the addition
was completed, the reaction mixture was stirred under heating at
60.degree. C. for 1 hour and a Grignard reagent was prepared.
[0149] In a 300 ml four-necked flask, 4.8 g (10 mmole) of
Intermediate Compound E, 0.28 g (0.4 mmole) of
PdCl.sub.2(PPh.sub.3).sub.2 and 1.0 ml (1 mmole) of a 1.0 M toluene
solution of AlH(iso-Bu).sub.2 were dissolved in 50 ml of
tetrahydrofuran under an argon stream. To this was added the
Grignard reagent prepared above dropwise at the room temperature.
The temperature was elevated and the reaction mixture was heated
under refluxing for over night. After the reaction was completed,
the reaction liquid was cooled with ice water. Precipitated
crystals were separated by filtration and washed with acetone. The
obtained crude crystals were recrystallized from 100 ml of acetone
and 4.3 g of yellow powder was obtained. The powder was identified
to be Compound (38) by the measurement in accordance with NMR, IR
and FD-MS (the yield: 60%).
SYNTHESIS EXAMPLE 7 (COMPOUND (47))
[0150] Synthesis of Compound (47)
[0151] In a 100 ml two-necked flask, 2.4 g (10 mmole) of
6-aminochrysene was dissolved into 20 ml of methylene chloride. To
this was added 2.5 g (25 mmole) of acetic anhydride and the
resulting mixture was stirred at the room temperature for 1 hour.
Then, the reaction solvent was removed by distillation and an oily
compound was obtained. In a 300 ml two-necked flask, 4.1 g (20
mmole) of iodobenzene, 3 g (30 mmole) of potassium carbonate and
0.06 g (1 mmole) of copper powder were dissolved in 100 ml of
nitrobenzene. To this was added the oily compound and the resulting
mixture was stirred under heating at 220.degree. C. for 2 days.
Then, the solvent was removed by distillation and 10 ml of
diethylene glycol and a solution prepared by dissolving 30 g of
potassium hydroxide into 100 ml of water were added to the residue.
The reaction was allowed to proceed at 110.degree. C. for one
night. After the reaction was completed, a mixture of ethyl acetate
and water was added to the reaction mixture. After the organic
layer was separated, the solvent was removed by distillation and
crude crystals were obtained.
[0152] Subsequently, in a 300 ml two-necked flask, the crude
crystals obtained above, 2 g (5 mmole) of 4,4'-diiodobiphenyl, 3 g
(30 mmole) of potassium carbonate and 0.06 g (1 mmole) of copper
powder were dissolved in 100 ml of nitrobenzene and the resulting
mixture was stirred under heating at 230.degree. C. for 2 days.
After the reaction was completed, precipitated crystals were
separated by filtration, washed with methanol, dried and purified
in accordance with the column chromatography (silica gel,
hexane/toluene=1/3) and 0.8 g of yellow powder was obtained. The
powder was identified to be Compound (47) by the measurements in
accordance with NMR, IR and FD-MS (the yield: 30%).
EXAMPLE 18
[0153] A cleaned glass plate having an ITO electrode was coated
with a composition which contained Compound (30) obtained above as
the light emitting material, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole
and a polycarbonate resin (manufactured by TEIJIN KASEI Co., Ltd.;
PANLITE K-1300) in amounts such that the ratio by weight was 5:3:2
and was dissolved in tetrahydrofuran in accordance with the spin
coating and a light emitting layer having a thickness of 100 nm was
obtained. On the obtained light emitting layer, an electrode having
a thickness of 150 nm was formed with an alloy prepared by mixing
aluminum and lithium in amounts such that the content of lithium
was 3% by weight and an organic EL device was obtained. The organic
EL device exhibited a luminance of emitted light of 320
(cd/m.sup.2), the maximum luminance of 14,000 (cd/m.sup.2) and an
efficiency of light emission of 2.5 (lm/W) under application of a
direct current voltage of 5 V.
EXAMPLE 19
[0154] On a cleaned glass plate having an ITO electrode, Compound
(37) obtained above was vacuum vapor deposited as the light
emitting material and a light emitting layer having a thickness of
100 nm was formed. On the layer formed above, an inorganic electron
injecting layer having a thickness of the film of 0.3 nm was formed
with lithium fluoride. Then, an electrode having a thickness of 100
nm was formed with aluminum and an organic EL device was obtained.
The light emitting layer was formed by vapor deposition under a
vacuum of 10.sup.-6 Torr while the temperature of the substrate was
kept at the room temperature. The organic EL device exhibited a
luminance of emitted light of about 110 (cd/m.sup.2), the maximum
luminance of 20,000 (cd/m.sup.2) and an efficiency of light
emission of 1.2 (lm/W) under application of a direct current
voltage of 5 V.
EXAMPLE 20
[0155] On a cleaned glass plate having an ITO electrode, CuPc was
vacuum vapor deposited as the hole injecting material and a hole
injecting layer having a thickness of 40 nm was formed. Then, a
hole transporting layer having a thickness of 20 nm was formed by
using Compound (47) obtained above as the hole transporting
material and a light emitting layer having a thickness of 60 nm was
formed by vacuum vapor deposition of the compound (Alq) described
above. Rubrene was added to the light emitting layer in an amount
of 4% by weight. On the layers formed above, an electrode having a
thickness of 100 nm was formed with an alloy prepared by mixing
aluminum and lithium in amounts such that the content of lithium
was 3% by weight and an organic EL device was obtained. The above
layers were formed by vapor deposition under a vacuum of 10.sup.-6
Torr while the temperature of the substrate was kept at the room
temperature. The organic EL emitted green light with a luminance of
emitted light of about 700 (cd/m.sup.2), the maximum luminance of
80,000 (cd/m.sup.2) and an efficiency of light emission of 6.0
(lm/W) under application of a direct current voltage of 5 V. When
the organic EL device was driven by a constant electric current at
an initial luminance of emitted light of 600 (cd/m.sup.2), the half
life time was as long as 4,000 hours.
EXAMPLES 21 TO 33
[0156] On a cleaned glass plate having an ITO electrode, a hole
injecting layer having a thickness of 20 nm was formed by vacuum
vapor deposition of the hole injecting material shown in Table 2. A
light emitting layer having a thickness of 60 nm was formed by
vapor deposition of the compound (Alq) described above as the light
emitting material and rubrene was added to the light emitting layer
in an amount of 4% by weight. On the layers formed above, an
electrode having a thickness of 15.0 nm was formed with an alloy
prepared by mixing aluminum and lithium in amounts such that the
content of lithium was 3% by weight. Organic EL devices were
obtained in this manner. The above layers were formed by vapor
deposition under a vacuum of 10.sup.-6 Torr while the temperature
of the substrate was kept at the room temperature. The light
emitting properties of the obtained devices are shown in Table 2.
The organic EL devices in these Examples all showed excellent
luminances such as the maximum luminance of 10,000 (cd/m.sup.2) or
greater. TABLE-US-00002 TABLE 2 Type of hole Half life time Example
transporting material (hour) 21 (30) 5200 22 (36) 5600 23 (37) 4200
24 (38) 3200 25 (41) 4800 26 (43) 6700 27 (48) 2400 28 (49) 5700 29
(50) 5200 30 (51) 6000 31 (53) 4000 32 (55) 4000 33 (56) 3200
EXAMPLE 34
[0157] On a cleaned glass plate having an ITO electrode, compound
(TPD74) described above was vacuum vapor deposited as the hole
injecting material and a layer having a thickness of 60 nm was
formed. Then, the compound (NPD) obtained above was vacuum vapor
deposited as the hole transporting material and a layer having a
thickness of 20 nm was formed.
[0158] 4,4'-bis(2,2-Diphenylvinyl)phenylanthracene (DPVDPAN) as the
light emitting material and Compound (36) described above as the
dopant were vapor deposited simultaneously and a layer which had a
content of Compound (36) of 2% by weight and a thickness of 40 nm
was formed. Then, the compound (Alq) described above was vapor
deposited as the charge injecting material and a layer having a
thickness of 20 nm was formed. After lithium fluoride was vapor
deposited and a layer having a thickness of 0.5 nm was formed,
aluminum was vapor deposited and an electrode having a thickness
was 100 nm formed. Thus, an organic EL device was obtained. The
above layers were formed by vapor deposition under a vacuum of
10.sup.-6 Torr while the temperature of the substrate was kept at
the room temperature. The organic EL device exhibited a luminance
of emitted light as high as 500 (cd/m.sup.2) under application of a
direct current voltage of 8 V and the emitted light had blue color
of excellent purity. When the organic EL device was driven by a
constant electric current at an initial luminance of emitted light
of 100 (cd/m.sup.2), the half life time was as long as 7,000
hours.
[0159] The spectrum of the light emitted by this device was
measured and it was found that the spectrum was the same as that of
the device using DPVBi. This means that Compound (36) did not
affect the light emission but exhibited the effect of extending the
life of the device.
COMPARATIVE EXAMPLE 3
[0160] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 34 except that
Compound (36) described above was not added as the dopant. When the
prepared organic EL device was driven by a constant electric
current at an initial luminance of emitted light of 100
(cd/m.sup.2), the half life time was shorter than the half life
time in Example 34, i.e., 4,000 hours.
COMPARATIVE EXAMPLE 4
[0161] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 20 except that
Compound of Comparative Example 2 described above was used as the
hole transporting material.
[0162] The prepared organic EL device exhibited a luminance of
emitted light of 300 (cd/m.sup.2) and an efficiency of light
emission of 4.2 (lm/W) under application of a direct current
voltage of 5 V. However, when the organic EL device was driven by a
constant electric current at an initial luminance of emitted light
of 400 (cd/m.sup.2), the half life time was as short as 300
hours.
Test of Heat Resistance
[0163] The organic EL devices prepared in Examples 20 and 27 and
Comparative Example 4, which had been used for the measurement of
luminance of emitted light, were placed in a chamber kept at the
constant temperature of 105.degree. C. After 500 hours, luminance
of light emission was measured again. The values of luminance
before and after the devices were kept in the chamber were compared
and the retention of luminance was calculated.
[0164] The retentions of luminance of the organic EL devices
prepared in Examples 20 and 27 and Comparative Example 4 thus
obtained were 87%, 90% and 25%, respectively. As shown by this
result, the compounds used as the light emitting material in
Comparative Example 4 could not retain luminance because the
compounds had a glass transition temperature lower than 105.degree.
C. In contrast, the compounds used for the light emitting material
in Examples 20 and 27 exhibited excellent heat resistance and could
retain luminance for a long time because the compounds had glass
transition temperatures higher than 110.degree. C.
SYNTHESIS EXAMPLE 8 (COMPOUND (58))
[0165] Synthesis of Intermediate Compound F
(5,11-dibromonaphthacene)
[0166] In a 2 liter round bottom flask, 50 g (0.19 mmole) of
5,12-naphthacene, 108 g (0.57 mmole) of tin(IV) chloride, 500 ml of
acetic acid and 200 ml of concentrated hydrochloric acid were
placed. The resulting mixture was stirred for reflux for 2 hours.
After the reaction was completed, precipitated crystals were
separated by filtration, washed with water and dried in a vacuum
drying chamber and 48 g of crude crystals were obtained.
[0167] Subsequently, in a 2 liter four-necked flask, the crude
crystals obtained above and 50 g (0.19 mmole) of triphenylphosphine
were dissolved in 300 ml of dimethylformamide under an argon
stream. To this was added 64 g (0.4 mmole) of bromine dissolved in
200 ml of dimethylformamide slowly dropwise and the resulting
mixture was stirred at ambient temperature. After the addition was
completed, the mixture was stirred under heating at 200.degree. C.
for one night. After the reaction was completed, dimethylformamide
was removed by distillation in vacuo and 200 ml of water was added
to the residue. The organic layer was extracted with toluene. The
extract was dried with magnesium sulfate and concentrated in vacuo
using a rotary evaporator and an oily compound was obtained. The
oily compound was purified in accordance with the column
chromatography (silica gel, hexane/toluene=1/1) and 30 g of yellow
powder was obtained. The powder was identified to be Intermediate
Compound F by the measurements in accordance with NMR, IR and FD-MS
(the yield: 40%).
[0168] Synthesis of Compound (58)
[0169] In a 100 ml two-necked flask, 2 g (10 mmole) of
4-aminostilbene was dissolved in 20 ml of methylene chloride. To
this was added 2.5 g (25 mmole) of acetic anhydride and the
resulting mixture was stirred at the room temperature for 1 hour.
Then, the reaction solvent was removed by distillation and an oily
compound was obtained. In a 300 ml two-necked flask, 4.1 g (20
mmole) of iodobenzene, 3 g (30 mmole) of potassium carbonate, 0.06
g (1 mmole) of copper powder and 100 ml of nitrobenzene were added
to the obtained oily compound and the obtained mixture was stirred
under heating at 220.degree. C. for 2 days. Then, the solvent was
removed by distillation and 10 ml of diethylene glycol and a
solution prepared by dissolving 30 g of potassium hydroxide into
100 ml of water were added to the residue. The reaction was allowed
to proceed at 110.degree. C. for one night. After the reaction was
completed, a mixture of ethyl acetate and water was added to the
reaction mixture. After the organic layer was separated, the
solvent was removed and crude crystals were obtained.
[0170] Subsequently, in a 100 ml two-necked flask, the crude
crystals obtained above, 1.9 g (5 mmole) of Intermediate Compound
F, 1.3 g (12 mmole) of potassium t-butoxide and 40 mg (5% by mole)
of PdCl.sub.2(PPh.sub.3).sub.2 were dissolved in 30 ml of xylene
under an argon stream. The resulting mixture was stirred under
heating at 130.degree. C. for over night. After the reaction was
completed, precipitated crystals were separated by filtration,
washed with methanol, dried and purified in accordance with the
column chromatography (silica gel, hexane/toluene=1/1) and 0.9 g of
yellow powder was obtained. The powder was identified to be
Compound (58) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 25%).
SYNTHESIS EXAMPLE 9
[0171] Synthesis of Compound (59)
[0172] In a 300 ml four-necked flask, 2 g (10 mmole) of
4-hydroxystilbene and 5.2 g (20 mmole) of triphenylphosphine were
dissolved in 50 ml of dimethylformamide under an argon stream. To
this mixture was added 5 g (20 mmole) of iodine dissolved in 50 ml
of dimethylformamide slowly dropwise at the room temperature and
the reaction was allowed to proceed. After the addition was
completed, the reaction mixture was stirred at 200.degree. C. for
over night. After the reaction was completed, dimethylformamide was
removed by distillation in vacuo and 200 ml of water was added to
the residue. The organic layer was extracted with toluene. The
extract was dried with magnesium sulfate and concentrated in vacuo
using a rotary evaporator and an oily compound was obtained. The
oily compound was purified in accordance with the column
chromatography (silica gel, hexane/toluene=1/1) and 2.5 g of yellow
powder was obtained.
[0173] Separately, in a 100 ml two-necked flask, 2 g (10 mmole) of
4-aminostilbene was dissolved in 20 ml of methylene chloride. To
this was added 2.5 g (25 mmole) of acetic anhydride and the
resulting mixture was stirred at the room temperature for 1 hour.
Then, the reaction solvent was removed by distillation and an oily
compound was obtained.
[0174] In a 300 ml two-necked flask, 2.5 g of the yellow powder
obtained above, 3 g (30 mmole) of potassium carbonate, 0.06 g (1
mmole) of copper powder and 100 ml of nitrobenzene were added to
the above oily compound. The resulting mixture was stirred under
heating at 220.degree. C. for 2 days. To the residue obtained by
removing the solvent from the above mixture by distillation, 10 ml
of diethylene glycol and 30 g of potassium hydroxide dissolved in
100 ml of water were added and the reaction was allowed to proceed
at 110.degree. C. for over night. After the reaction was completed,
a mixture of ethyl acetate and water was added to the reaction
mixture. After the organic layer was separated, the solvent was
removed by distillation and crude crystals were obtained.
[0175] Subsequently, in a 300 ml two-necked flask, the above crude
crystals, 2.4 g (5 mmole) of Intermediate Compound F, 1.3 g (12
mmole) of potassium t-butoxide and 40 mg (5% by mole) of
PdCl.sub.2(PPh.sub.3).sub.2 were dissolved in 30 ml of xylene under
an argon stream. The resulting mixture was stirred under heating at
130.degree. C. and the reaction was allowed to proceed for over
night. After the reaction was completed, precipitated crystals were
separated by filtration, washed with methanol, dried and purified
by the column chromatography (silica gel, hexane/toluene=1/1) and
0.2 g of yellow powder was obtained. The powder was identified to
be Compound (59) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 5%).
SYNTHESIS EXAMPLE 10 (COMPOUND (61))
[0176] Synthesis of Compound (61)
[0177] In a 300 ml four-necked flask, 9.7 g (30 mmole) of
4-bromotriphenylamine, 50 ml of toluene and 50 ml of diethyl ether
were placed and the resulting mixture was cooled with ice water
under an argon stream. To the cooled mixture, a mixture of 22 ml
(33 mmole) of a hexane solution (1.52 mole/liter) of n-butyllithium
and 100 ml of tetrahydrofuran were slowly added dropwise at the
room temperature and the resulting mixture was stirred. After 4.3 g
(10 mmole) of 6,13-dibromopenthacene was added to the reaction
mixture, the obtained mixture was stirred at the same temperature
for one night. After the reaction was completed, 500 ml of water
was added to the reaction mixture and the organic layer was
extracted with diethyl ether. The extract was dried with magnesium
sulfate and concentrated in vacuo using a rotary evaporator and 7.4
g of an oily compound was obtained.
[0178] In a 300 ml four-necked flask, the above compound, 6.6 g (40
mmole) of potassium iodide and 100 ml of acetic acid were placed
and the resulting mixture was heated under refluxing for 1 hour.
After the reaction was completed, the reaction mixture was cooled
to the room temperature and precipitated crystals were separated by
filtration. The obtained crystals were washed with water and
acetone and 2.7 g of orange solid was obtained. The orange solid
was identified to be Compound (61) by the measurement in accordance
with NMR, IR and FD-MS (the yield: 35%).
SYNTHESIS EXAMPLE 11 (COMPOUND (62))
[0179] Synthesis of Intermediate Compound G
(5,11-diiodonaphthacene)
[0180] In a 500 ml round bottom flask, 50 g (0.22 mmole) of
naphthacene and 200 ml of tetrachloroethane were placed. To this
was added 160 g (0.64 mole) of iodine dissolved in 200 ml of carbon
tetrachloride slowly dropwise at the room temperature and the
resulting mixture was stirred under heating for 5 hours.
Precipitated crystals were separated by filtration and washed with
500 ml of methanol. The obtained crude crystals were recrystallized
from 200 ml of toluene and 34 g of Intermediate Compound G was
obtained (the yield: 40%).
[0181] Synthesis of Compound (62)
[0182] In a 100 ml four-necked flask, 1.0 g (41 mmole) of
magnesium, 1 ml of tetrahydrofuran and a small piece of iodine were
placed under an argon stream. To this was added 9.7 g (30 mmole) of
4-bromotriphenylamine dissolved in 100 ml of tetrahydrofuran slowly
dropwise at the room temperature. After the addition was completed,
the resulting mixture was stirred under heating at 60.degree. C.
for 1 hour and a Grignard reagent was prepared.
[0183] In a 300 ml four-necked flask, 4.8 g (10 mmole) of
Intermediate Compound G, 0.28 g (0.4 mmole) of
PdCl.sub.2(PPh.sub.3).sub.2 and 1.0 ml (1 mmole) of a 1.0 M toluene
solution of AlH(iso-Bu).sub.2 were dissolved in 50 ml of
tetrahydrofuran under an argon stream. To the this mixture, the
Grignard reagent prepared above was added dropwise at the room
temperature. The temperature was elevated and the reaction mixture
was heated under refluxing for one night. After the reaction was
completed, the reaction liquid was cooled with ice water.
Precipitated crystals were separated by filtration and washed with
acetone. The obtained crude crystals were recrystallized from 100
ml of acetone and 3.6 g of yellow powder was obtained. The powder
was identified to be Compound (62) by the measurement in accordance
with NMR, IR and FD-MS (the yield: 50%).
EXAMPLE 35
[0184] A cleaned glass plate having an ITO electrode was coated
with a composition which contained Compound (58) obtained above as
the light emitting material, 2,5-bis(1-naphthyl)-1,3,4-oxadiazole
and a polycarbonate resin (manufactured by TEIJIN KASEI Co., Ltd.;
PANLITE K-1300) in amounts such that the ratio by weight was 5:2:2
and was dissolved in tetrahydrofuran in accordance with the spin
coating and a light emitting layer having a thickness of 100 nm was
obtained. On the obtained light emitting layer, an electrode having
a thickness of 150 nm was formed with an alloy prepared by mixing
aluminum and lithium in amounts such that the content of lithium
was 3% by weight and an organic EL device was obtained. The organic
EL device emitted yellowish orange light with a luminance of
emitted light of 130 (cd/m.sup.2), the maximum luminance of 14,000
(cd/m.sup.2) and an efficiency of light emission of 1.2 (lm/W)
under application of a direct current voltage of 5 V.
EXAMPLE 36
[0185] On a cleaned glass plate having an ITO electrode, Compound
(71) obtained above was vacuum vapor deposited as the light
emitting material and a light emitting layer having a thickness of
100 nm was prepared. On the obtained light emitting layer, an
electrode having a thickness of 100 nm was formed with an alloy
prepared by mixing aluminum and lithium in amounts such that the
content of lithium was 3% by weight and an organic EL device was
obtained. The light emitting layer was formed by vapor deposition
under a vacuum of 10.sup.-6 Torr while the temperature of the
substrate was kept at the room temperature. The organic EL device
emitted orange light with a luminance of emitted light of 120
(cd/m.sup.2), the maximum luminance of 1,800 (cd/m.sup.2) and an
efficiency of light emission of 0.3 (lm/W) under application of a
direct current voltage of 5 V.
EXAMPLE 37
[0186] On a cleaned glass plate having an ITO electrode, Compound
(71) obtained above was vacuum vapor deposited as the light
emitting material and a light emitting layer having a thickness of
50 nm was prepared. Then, the compound (Alq) described above was
vacuum vapor deposited on the obtained light emitting layer and an
electron injection layer having a thickness of 10 nm was formed. On
the formed layer, an electrode having a thickness of 100 nm was
formed with an alloy prepared by mixing aluminum and lithium in
amounts such that the content of lithium was 3% by weight and an
organic EL device was obtained. The light emitting layer and the
electron injecting layer were formed by vapor deposition under a
vacuum of 10.sup.-6 Torr while the temperature of the substrate was
kept at the room temperature. The organic EL device emitted orange
light with a luminance of emitted light of about 200 (cd/m.sup.2),
the maximum luminance of 12,000 (cd/m.sup.2) and an efficiency of
light emission of 1.0 (lm/W) under application of a direct current
voltage of 5 V.
EXAMPLES 38 TO 46
[0187] On a cleaned glass plate having an ITO electrode, a light
emitting material shown in Table 3 was vacuum vapor deposited and a
light emitting layer having a thickness of 80 nm was prepared.
Then, the compound (Alq) described above was vacuum vapor deposited
on the obtained light emitting layer and an electron injecting
layer having a thickness of 20 nm was formed. On the formed layer,
an electrode having a thickness of 150 nm was formed with an alloy
prepared by mixing aluminum and lithium in amounts such that the
content of lithium was 3% by weight. In this manner, organic EL
devices were obtained. The above layers were formed by vapor
deposition under a vacuum of 10.sup.-6 Torr while the temperature
of the substrate was kept at the room temperature. The properties
of light emission of the obtained organic EL devices are shown in
Table 3. The organic EL devices in these Examples all showed
excellent luminances such as the maximum luminance of 5,000
(cd/m.sup.2) or greater. TABLE-US-00003 TABLE 3 Efficiency of Type
of light emitting light emission Half life time Example material
(lm/W) (hour) 38 (59) 1.2 1400 39 (60) 1.4 1600 40 (61) 0.7 1700 41
(62) 0.8 850 42 (65) 0.4 1200 43 (67) 0.6 1700 44 (70) 1.6 2400 45
(72) 1.2 1600 46 (74) 0.5 1200
EXAMPLE 47
[0188] On a cleaned glass plate having an ITO electrode, the
compound (TPD74) described above was vacuum vapor deposited as the
hole injecting material and a layer having a thickness of 60 nm was
formed. Then, the compound (NPD) described later was vapor
deposited as the hole transporting material and a layer having a
thickness of 20 nm was formed.
[0189] Then, 4,4'-bis(2,2-diphenylvinyl)biphenyl (DPVBi) and
Compound (58) described above were simultaneously vacuum deposited
as the light emitting materials and a layer having a content of
Compound (58) of 5% by weight and a thickness of 40 nm was formed.
Compound (58) worked also as a fluorescent dopant. Then, the
compound (Alq) described above was vapor deposited as the election
injection material and a layer having a thickness of 20 nm was
formed. On the formed layer, lithium fluoride was vapor deposited
and a layer having a thickness of 0.5 nm was formed. Then, aluminum
was vapor deposited and a layer having a thickness of 100 nm was
formed. Thus, an electrode was formed and an organic EL device was
obtained. The above layers were formed by vapor deposition under a
vacuum of 10.sup.-6 Torr while the temperature of the substrate was
kept at the room temperature. The organic EL device emitted yellow
light with a luminance of emitted light of about 600 (cd/m.sup.2)
under application of a direct current voltage of 5 V. When the
organic EL device was driven by a constant electric current at an
initial luminance of emitted light of 400 (cd/m.sup.2), the half
life time was as long as 2,800 hours.
EXAMPLE 48
[0190] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 47 except that the
light emitting layer was formed by simultaneously vapor depositing
the compound (Alq) described above as the light emitting material
and Compound (61) described above as the dopant and a light
emitting layer having the content of Compound (61) of 5% by weight
was formed. The organic EL device emitted red light with a
luminance of emitted light of about 240 (cd/m.sup.2) under
application of a direct current voltage of 5 V. When the organic EL
device was driven by a constant electric current at an initial
luminance of emitted light of 400 (cd/m.sup.2), the half life time
was as long as 3,200 hours.
COMPARATIVE EXAMPLE 5
[0191] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 35 except that
(Compound of Comparative Example 1) described above was used as the
light emitting material.
[0192] The organic EL device exhibited luminance of emitted light
of about 60 (cd/m.sup.2) and an efficiency of light emission of
0.34 (lm/W) under application of a direct current voltage of 5 V.
Sufficient properties could not be obtained. The emitted light was
blue light.
COMPARATIVE EXAMPLE 6
[0193] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 37 except that
(Compound of Comparative Example 2) described above was used as the
light emitting material.
[0194] The organic EL device exhibited a luminance of emitted light
of about 200 (cd/m.sup.2) and an efficiency of light emission of
1.2 (lm/W) under application of a direct current voltage of 5 V.
However, when the organic EL device was driven by a constant
electric current at an initial luminance of emitted light of 400
(cd/m.sup.2), the half life time was as short as 600 hours. The
emitted light was blue light.
COMPARATIVE EXAMPLE 7
[0195] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 47 except that
(Compound of Comparative Example 1) described above was used in
place of Compound (58).
[0196] The organic EL device exhibited a luminance of emitted light
of about 200 (cd/m.sup.2) under application of a direct current
voltage of 5 V. However, when the organic EL device was driven by a
constant electric current at an initial luminance of emitted light
of 400 (cd/m.sup.2), the half life time was as short as 700 hours.
The emitted light was blue light.
SYNTHESIS EXAMPLE 12 (COMPOUND (75))
[0197] Synthesis of Compound (75)
[0198] In a 200 ml three-necked flask, 2.16 g (5.5 mmole) of
6,12-dibromonaphthacene (40577-78-4), 0.06 g (0.3 mmole) of
Pd(OAc).sub.2, 0.23 g (1.1 mmole) of P(tBu).sub.3, 1.51 g (15.7
mmole) of NaOtBu and 1.89 g (11.2 mmole) of Ph.sub.2NH were
dissolved in 25 ml of toluene under an argon stream. The resulting
mixture was stirred under heating at 120.degree. C. and the
reaction was allowed to proceed for 7 hours. After the reaction was
completed, the reaction mixture was left standing and cooled. After
red crystals were separated by filtration, the crystals were washed
with toluene and water and dried in vacuo and 3.02 g of red powder
was obtained. The powder was identified to be Compound (75) by the
measurements in accordance with NMR, IR and FD-MS (the yield: 96%).
The data obtained in NMR (CDCl.sub.3, TMS) were as follows:
6.8.about.7.0 (m, 2H), 7.0.about.7.4 (m, 10H), 7.8.about.7.9 (m,
1H), 8.0.about.8.1 (m, 1H) and 8.85 (s, 1H).
EXAMPLE 49
[0199] On a cleaned glass plate having an ITO electrode, Compound
(TPD74) described above was vacuum vapor deposited as the hole
injecting material and a layer having a thickness of 60 nm was
formed. Then, the compound (NPD) described above was vacuum vapor
deposited as the hole transporting material and a layer having a
thickness of 20 nm was formed.
[0200] Then, the compound (Alq) described above as the light
emitting material and Compound (75) described above as the dopant
were simultaneously vapor deposited and a layer having a content of
Compound (75) of 2% by weight and a thickness of 40 nm was formed.
Then, the compound (Alq) described above was vapor deposited as the
electron injecting material and a layer having a thickness of 20 nm
was formed. After lithium fluoride was vapor deposited and a layer
having a thickness of 20 nm was formed, aluminum was vapor
deposited and a layer having a thickness of 100 nm was formed.
Thus, an electrode was formed and an organic EL device was
prepared. The above layers were formed by vapor deposition under a
vacuum of 10.sup.-6 Torr while the temperature of the substrate was
kept at the room temperature. The organic EL device exhibited a
luminance of emitted light as high as 500 (cd/m.sup.2) under
application of a direct current voltage of 8 V and the emitted
light was orange light. The organic EL device exhibited a luminance
of emitted light as high as 500 (cd/m.sup.2) under application of a
direct current voltage of 8 V and the emitted light was orange
light. When the organic EL device was driven by a constant electric
current at an initial luminance of emitted light of 500
(cd/m.sup.2), the organic EL device had a particularly long half
life time, which was longer than 2,000 hours.
EXAMPLE 50
[0201] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 49 except that
Compound (86) described above was used as the dopant in place of
Compound (75). When the organic EL device was driven by a constant
electric current at an initial luminance of emitted light of 500
(cd/m.sup.2), the organic EL device had a half life time as long as
2,000 hours. The emitted light was vermilion light.
EXAMPLE 51
[0202] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 49 except that
Compound (82) described above was used as the dopant in place of
Compound (75). The organic EL device exhibited an initial luminance
of emitted light of 500 (cd/m.sup.2) and the organic EL device had
a half life time as long as 2,800 hours or longer when the organic
EL device was driven by a constant electric current. The emitted
light was red light.
SYNTHESIS EXAMPLE 13 (COMPOUND (100))
[0203] Synthesis of Intermediate Compound H
[0204] In a 1 liter three-necked flask equipped with a condenser,
22.7 g (0.1 mole) of 4-bromophthalic anhydride and 42.4 g (0.4
mole) of sodium carbonate were suspended in 300 ml of water and the
components were dissolved by heating at 60.degree. C. under an
argon stream. After the mixture was dissolved, the resulting
mixture was cooled to the room temperature. To the cooled mixture,
18.3 g (0.15 mole) of phenylboric acid and 0.7 g (3% by mole) of
palladium acetate were added and the obtained mixture was stirred
at the room temperature for one night. After the reaction was
completed, separated crystals were dissolved by adding water. After
the catalyst was removed by filtration, crystals were precipitated
by adding concentrated hydrochloric acid. The crystals were
separated by filtration and washed with water. The obtained
crystals was dissolved in ethyl acetate and the organic layer was
extracted. The extract was dried with magnesium sulfate and
concentrated in vacuo using a rotary evaporator and 23.7 g (the
yield: 98%) of Intermediate Compound H of the object compound was
obtained.
[0205] Synthesis of Intermediate Compound I
[0206] In a 500 ml flask having an egg plant shape and equipped
with a condenser, 23.7 g (98 mmole) of Intermediate Compound H and
200 ml of acetic anhydride were placed and the resulting mixture
was stirred at 80.degree. C. for 3 hours. After the reaction was
completed, acetic anhydride in an excess amount was removed by
distillation and 22 g (the yield: 10%) of Intermediate Compound I
of the object compound was obtained.
[0207] Synthesis of Intermediate Compound J
[0208] In a 500 ml three-necked flask equipped with a condenser,
7.7 g (50 mmole) of biphenyl, 13.4 g (0.1 mole) of anhydrous
aluminum chloride and 200 ml of 1,2-dichloroethane were placed
under an argon stream and the resulting mixture was cooled to
0.degree. C. To the cooled mixture, 22 g (98 mmole) of Intermediate
Compound I was slowly added and the resulting mixture was stirred
at 40.degree. C. for 2 hours. After the reaction was completed, ice
water was added to the reaction mixture and the resulting mixture
was extracted with chloroform. The extract was dried with magnesium
sulfate and concentrated in vacuo using a rotary evaporator and
19.0 g (the yield: 100%) of Intermediate Compound J of the object
compound was obtained.
[0209] Synthesis of Intermediate Compound K
[0210] In a 500 ml flask having an egg plant shape and equipped
with a condenser, 200 ml of polyphosphoric acid was placed and
heated to 150.degree. C. Then, 19 g (50 mmole) of Intermediate
Compound J was added in small portions and the resulting mixture
was stirred at the same temperature for 3 hours. After the reaction
was completed, ice water was added to the reaction mixture and the
resulting mixture was extracted with chloroform. The extract was
dried with magnesium sulfate and concentrated in vacuo using a
rotary evaporator. The obtained crude crystals were purified in
accordance with the column chromatography (silica gel,
chloroform/methanol=99/1) and 19 g (the yield: 55%) of Intermediate
Compound K of the object compound was obtained.
[0211] Synthesis of Intermediate Compound L
[0212] In a 500 ml flask having an egg plant shape and equipped
with a condenser, 19.0 g (28 mmole) of Intermediate Compound K,
0.19 g (1 mmole) of tin chloride, 100 ml of acetic acid and 50 ml
of concentrated hydrochloric acid were placed under an argon stream
and the resulting mixture was heated under refluxing for 2 hours.
After the reaction was completed, the reaction mixture was cooled
with ice water and precipitated crystals were separated, washed
with water to give 19 g (the yield: 100%) of Intermediate Compound
L of the object compound.
[0213] Synthesis of Intermediate Compound M
[0214] In a 500 ml three-necked flask equipped with a condenser,
19.0 g (28 mmole) of Intermediate Compound L, 16 g (60 mmole) of
triphenylphosphine and 200 ml of dimethylformamide were placed
under an argon stream. To this was added 9.6 g (60 mmole) of iodine
dissolved in 50 ml of dimethylformamide slowly dropwise and the
resulting mixture was stirred under heating at 200.degree. C. for 8
hours. After the reaction was completed, the reaction mixture was
cooled with ice water and precipitated crystals were separated. The
obtained crystals were washed with water and methanol and 6.7 g
(the yield: 50%) of Intermediate Compound M of the object compound
was obtained.
[0215] Synthesis of Compound (100)
[0216] In a 200 ml three-necked flask equipped with a condenser,
4.9 g (10 mmole) of Intermediate Compound M, 5.1 g (30 mmole) of
diphenylamine, 0.14 g (1.5% by mole) of
tris(dibenzylideneacetone)-dipalladium, 0.91 g (3% by mole) of
tri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxide and 50
ml of dry toluene were placed under an argon stream. The resulting
mixture was stirred overnight under heating at 100.degree. C. After
the reaction was completed, precipitated crystals were separated by
filtration and washed with 100 ml of methanol and 4.0 g of yellow
powder was obtained. The obtained powder was identified to be
Compound (100) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 60%).
[0217] The chemical structures of Intermediate Compounds and the
route of synthesis of Compound (100) are shown in the following.
##STR72## ##STR73##
SYNTHESIS EXAMPLE 14 (COMPOUND (101))
[0218] Synthesis of Intermediate Compound N
[0219] In a 500 ml flask having an egg plant shape and equipped
with a condenser, 12 g (50 mmole) of 2,6-dihydroxyanthraquinone,
42.5 g (0.3 mole) of methyl iodide, 17 g (0.3 mole) of potassium
hydroxide and 200 ml of dimethylsulfoxide were placed under an
argon stream and the resulting mixture was stirred at the room
temperature for 2 hours. After the reaction was completed,
precipitated crystals were separated by filtration. The obtained
crystals were washed with 100 ml of methanol and 10.7 g (the yield:
80%) of Intermediate Compound N of the object compound was
obtained.
[0220] Synthesis of Intermediate Compound O
[0221] In a 500 ml three-necked flask equipped with a condenser,
10.7 g (40 mmole) of Intermediate Compound N and 200 ml of dry
tetrahydrofuran were placed under an argon stream and the resulting
mixture was cooled to -40.degree. C. To the cooled mixture, 53 ml
(80 mmole) of a 1.5 M hexane solution of phenyllithium was added
slowly dropwise. After the addition was completed, the reaction
mixture was stirred at the room temperature for one night. After
the reaction was completed, precipitated crystals were separated by
filtration and washed with 100 ml of methanol and 100 ml of
acetone. The obtained crude crystals of a diol was used in the
following reaction without further purification.
[0222] In a 500 ml flask having an egg plant shape and equipped
with a condenser, the crude crystals obtained above, 100 ml of a
57% aqueous solution of hydrogen iodide and 200 ml of acetic acid
were placed and the resulting mixture was heated under refluxing
for 3 hours. After the reaction was cooled to the room temperature,
a small amount of hypophosphorous acid was added to quench hydrogen
iodide in an excess amount. Precipitated crystals were separated by
filtration and washed with 100 ml of water, 100 ml of methanol and
100 ml of acetone, successively, and 10.1 g (the yield: 70%) of
Intermediate Compound O of the object compound was obtained.
[0223] Synthesis of Intermediate Compound P
[0224] In a 500 ml flask having an egg plant shape and equipped
with a condenser, 10.1 g (28 mmole) of Intermediate Compound O, 7.9
g (30 mmole) of triphenylphosphine and 200 ml of dimethylformamide
were placed under an argon stream. To the resulting mixture, 4.8 g
(30 mmole) of bromine dissolved in 50 ml of dimethylformamide was
slowly added dropwise and the obtained mixture was stirred under
heating at 200.degree. C. for 8 hours. After the reaction was
completed, the reaction mixture was cooled with ice water and
precipitated crystals were separated by filtration. The obtained
crystals were washed with water and methanol and 8.2 g (the yield:
60%) of Intermediate Compound P of the object compound was
obtained.
[0225] Synthesis of Compound (101)
[0226] In a 200 ml three-necked flask equipped with a condenser,
4.9 g (30 mmole) of Intermediate Compound P, 5.1 g (30 mmole) of
diphenylamine, 0.14 g (1.5% by mole) of
tris(dibenzylideneacetone)-dipalladium, 0.91 g (3% by mole) of
tri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxide and 50
ml of dry toluene were placed under an argon stream. The resulting
mixture was stirred overnight under heating at 100.degree. C. After
the reaction was completed, precipitated crystals were separated by
filtration and washed with 100 ml of methanol and 4.0 g of yellow
powder was obtained. The obtained powder was identified to be
Compound (101) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 60%).
[0227] The chemical structures of Intermediate Compounds and the
route of synthesis of Compound (101) are shown in the following.
##STR74##
SYNTHESIS EXAMPLE 15 (COMPOUND (93))
[0228] Synthesis of Intermediate Compound Q
[0229] In a 300 ml three-necked flask equipped with a condenser,
11.7 g (50 mmole) of 2-bromobiphenyl, 19 g (0.2 mole) of aniline,
0.69 g (1.5% by mole) of tris(dibenzylideneacetone)dipalladium,
0.46 g (3% by mole) of tri-o-toluylphosphine, 7.2 g (75 mmole) of
sodium t-butoxide and 100 ml of dry toluene were placed under an
argon stream. The resulting mixture was stirred overnight under
heating at 100.degree. C. After the reaction was completed,
precipitated crystals were separated by filtration and washed with
100 ml of methanol. The obtained crude crystals were recrystallized
from 50 ml of ethyl acetate and 9.8 g (the yield: 80%) of
Intermediate Compound Q of the object compound was obtained.
[0230] Synthesis of Compound (93)
[0231] In a 200 ml three-necked flask equipped with a condenser,
2.4 g (10 mmole) of 9,10-dibromoanthracene, 7.4 g (30 mmole) of
Intermediate Compound Q, 0.14 g (1.5% by mole) of
tris(dibenzylideneacetone)dipalladium, 0.91 g (3% by mole) of
tri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxide and 50
ml of dry toluene were placed under an argon stream. The resulting
mixture was stirred overnight under heating at 100.degree. C. After
the reaction was completed, precipitated crystals were separated by
filtration and washed with 100 ml of methanol and 4.3 g of yellow
powder was obtained. The obtained powder was identified to be
Compound (93) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 65%).
[0232] The chemical structure of Intermediate Compound and the
route of synthesis of Compound (93) are shown in the following.
##STR75##
SYNTHESIS EXAMPLE 16 (COMPOUND (95))
[0233] Synthesis of Intermediate Compound R
[0234] In a 1 liter three-necked flask equipped with a condenser,
34 g (0.2 mole) of 3-phenylphenol, 58 g (0.22 mmole) of
triphenylphosphine and 300 ml of dimethylformamide were placed
under an argon stream. To the resulting mixture, 35 g (0.22 mmole)
of bromine dissolved in 100 ml of dimethylformamide was slowly
added dropwise and the obtained mixture was stirred at 200.degree.
C. for 8 hours. After the reaction was completed, the reaction
mixture was cooled with ice water and precipitated crystals were
separated by filtration. The obtained crystals were washed with
water and methanol and 37 g (the yield: 80%) of Intermediate
Compound R of the object compound was obtained.
[0235] Synthesis of Intermediate Compound S
[0236] In a 300 ml three-necked flask equipped with a condenser, 19
g (0.2 mmole) of aniline, 0.69 g (1.5% by mole) of
tris(dibenzylideneacetone)dipalladium, 0.46 g (3% by mole) of
tri-o-toluylphosphine, 7.2 g (75 mmole) of sodium t-butoxide and
100 ml of dry toluene were placed under an argon stream. The
resulting mixture was stirred overnight under heating at
100.degree. C. After the reaction was completed, precipitated
crystals were separated by filtration and washed with 100 ml of
methanol. The obtained crude crystals were recrystallized from 50
ml of ethyl acetate and 9.8 g (the yield: 80%) of Intermediate
Compound S of the object compound was obtained.
[0237] Synthesis of Compound (95)
[0238] In a 200 ml three-necked flask equipped with a condenser,
2.4 g (10 mmole) of 9,10-dibromoanthracene, 7.4 g (30 mmole) of
Intermediate Compound S, 0.14 g (1.5% by mole) of
tris(dibenzylideneacetone)dipalladium, 0.91 g (3% by mole) of
tri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxide and 50
ml of dry toluene were placed under an argon stream. The resulting
mixture was stirred overnight under heating at 100.degree. C. After
the reaction was completed, precipitated crystals were separated by
filtration and washed with 100 ml of methanol and 4.2 g of yellow
powder was obtained. The obtained powder was identified to be
Compound (95) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 70%).
[0239] The chemical structures of Intermediate Compounds and the
route of synthesis of Compound (95) are shown in the following.
##STR76##
SYNTHESIS EXAMPLE 17 (COMPOUND (104))
[0240] Synthesis of Intermediate Compound T
[0241] In a 300 ml three-necked flask equipped with a condenser, 23
g (0.1 mole) of 4-bromobiphenyl, 9.8 g (50 mmole) of aminostilbene,
0.69 g (1.5% by mole) of tris(dibenzylideneacetone)dipalladium,
0.46 g (3% by mole) of tri-o-toluylphosphine, 7.2 g (75 mmole) of
sodium t-butoxide and 100 ml of dry toluene were placed under an
argon stream. The resulting mixture was stirred overnight under
heating at 100.degree. C. After the reaction was completed,
precipitated crystals were separated by filtration and washed with
100 ml of methanol. The obtained crude crystals were recrystallized
from 50 ml of ethyl acetate and 13.9 g (the yield: 80%) of
Intermediate Compound T of the object compound was obtained.
[0242] Synthesis of Compound (104)
[0243] Into a 200 ml three-necked flask equipped with a condenser,
2.4 g (10 mmole) of 9,10-dibromoanthracene, 7.4 g (30 mmole) of
Intermediate Compound T, 0.14 g (1.5% by mole) of
tris(dibenzylideneacetone)dipalladium, 0.91 g (3% by mole) of
tri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxide and 50
ml of dry toluene were placed under an argon stream. The resulting
mixture was stirred overnight under heating at 100.degree. C. After
the reaction was completed, precipitated crystals were separated by
filtration and washed with 100 ml of methanol and 4.5 g of yellow
powder was obtained. The obtained powder was identified to be
Compound (104) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 70%).
[0244] The chemical structure of Intermediate Compound and the
route of synthesis of Compound (104) are shown in the following.
##STR77##
SYNTHESIS EXAMPLE 18 (COMPOUND (105))
[0245] Synthesis of Intermediate Compound U
[0246] In a 500 ml three-necked flask equipped with a condenser, 25
g (0.1 mole) of triphenylamine, 18 g (0.1 mole) of
N-bromosuccimide, 0.82 g (5% by mole) of
2,2'-azobisisobutyronitrile and 200 ml of dimethylformamide were
placed under an argon stream. The resulting mixture was stirred
under heating at 110.degree. C. for 4 hours. After the reaction was
completed, impurities were removed by filtration and the filtrate
was concentrated in vacuo using a rotary evaporator. The obtained
crude crystals were purified in accordance with the column
chromatography (silica gel, methylene chloride) and 19 g (the
yield: 60%) of Intermediate Compound U of the object compound was
obtained.
[0247] Synthesis of Intermediate Compound V
[0248] In a 1 liter three-necked flask equipped with a condenser,
1.6 g (66 mmole) of magnesium, a small piece of iodine and 100 ml
of tetrahydrofuran were placed under an argon stream. After the
resulting mixture was stirred at the room temperature for 30
minutes, 19 g (60 mole) of Intermediate Compound U dissolved in 300
ml of tetrahydrofuran was added dropwise. After the addition was
completed, the reaction mixture was stirred under heating at
60.degree. C. for 1 hour and a Grignard reagent was prepared.
[0249] In a 1 liter three-necked flask equipped with a condenser,
42 g (0.18 mmole) of 1,3-dibromobenzene, 2.1 (5% by mole) of
dichlorobis(triphenylphosphine)palladium, 6 ml (6 mmole) of a 1 M
toluene solution of diisobutylaluminum hydride and 200 ml of
tetrahydrofuran were placed under an argon stream. To the mixture,
the Grignard reagent prepared above was added dropwise and the
obtained mixture was stirred under heating for one night. After the
reaction was completed, the reaction liquid was cooled with ice
water. Precipitated crystals were separated by filtration and
washed with acetone and 14 g (the yield: 60%) of Intermediate
Compound V of the object compound was obtained.
[0250] Synthesis of Compound (105)
[0251] In a 500 ml three-necked flask equipped with a condenser,
0.8 g (33 mmole) of magnesium, a small piece of iodine and 50 ml of
tetrahydrofuran were placed under an argon stream. After the
resulting mixture was stirred at the room temperature for 30
minutes, 12 g (30 mmole) of Intermediate Compound V dissolved in
100 ml of tetrahydrofuran was added dropwise. After the addition
was completed, the reaction mixture was stirred under heating at
60.degree. C. for 1 hour and a Grignard reagent was prepared.
[0252] In a 500 ml three-necked flask equipped with a condenser,
3.4 g (10 mmole) of 9,10-dibromoanthracene, 0.4 (5% by mole) of
dichlorobis(triphenylphosphine)palladium, 0.46 g (3% by mole) of
tri-o-toluylphosphine, 1 ml (1 mmole) of a 1 M toluene solution of
diisobutylaluminum hydride and 100 ml of tetrahydrofuran were
placed under an argon stream. To the obtained mixture, the Grignard
reagent prepared above was added dropwise at the room temperature
and the resulting mixture was refluxed overnight. After the
reaction was completed, the reaction liquid was cooled with ice
water. Precipitated crystals were separated by filtration and
washed with 50 ml of methanol and 50 ml of acetone, successively,
and 4.1 g of yellow powder was obtained. The obtained powder was
identified to be Compound (105) by the measurements in accordance
with NMR, IR and FD-MS (the yield: 50%).
[0253] The chemical structures of Intermediate Compounds and the
route of synthesis of Compound (105) are shown in the following.
##STR78##
SYNTHESIS EXAMPLE 19 (COMPOUND (122))
[0254] Synthesis of Intermediate Compound W
[0255] In a 300 ml three-necked flask equipped with a condenser, 19
g (80 mmole) of 1,3-dibromobenzene, 6.5 g (20 mmole) of
diphenylamine, 0.27 g (1.5% by mole) of
tris(dibenzylideneacetone)dipalladium, 0.18 g (3% by mole) of
tri-o-toluylphosphine, 2.9 g (30 mmole) of sodium t-butoxide and
100 ml of dry toluene were placed under an argon stream. The
resulting mixture was stirred overnight under heating at
100.degree. C. After the reaction was completed, precipitated
crystals were separated by filtration and washed with 100 ml of
methanol. The obtained crude crystals were recrystallized from 50
ml of ethyl acetate and 4.9 g (the yield: 75%) of Intermediate
Compound W of the object compound was obtained.
[0256] Synthesis of Compound (122)
[0257] In a 300 ml three-necked flask equipped with a condenser,
0.5 g (20 mmole) of magnesium, a small piece of iodine and 50 ml of
tetrahydrofuran were placed under an argon stream. After the
resulting mixture was stirred at the room temperature for 30
minutes, 4.9 g (15 mmole) of Intermediate Compound W dissolved in
100 ml of tetrahydrofuran was added dropwise. After the addition
was completed, the reaction mixture was stirred under heating at
60.degree. C. for 1 hour and a Grignard reagent was prepared.
[0258] In a 500 ml three-necked flask equipped with a condenser,
1.7 g (5 mmole) of 9,10-dibromoanthracene, 0.2 g (5% by mole) of
dichlorobis(triphenylphosphine)palladium, 0.5 ml (0.5 mmole) of a 1
M toluene solution of diisobutylaluminum hydride and 100 ml of
tetrahydrofuran were placed under an argon stream. To the mixture,
the Grignard reagent prepared above was added dropwise at the room
temperature and the resulting mixture was stirred overnight under
heating. After the reaction was completed, the reaction liquid was
cooled with ice water. Precipitated crystals were separated by
filtration and washed with 50 ml of methanol and 50 ml of acetone,
successively, and 1.7 g of yellow powder was obtained. The obtained
powder was identified to be Compound (122) by the measurements in
accordance with NMR, IR and FD-MS (the yield: 50%).
[0259] The chemical structure of Intermediate Compound and the
route of synthesis of Compound (122) are shown in the following.
##STR79##
SYNTHESIS EXAMPLE 20 (COMPOUND (123))
[0260] Synthesis of Intermediate Compound X
[0261] In a 300 ml three-necked flask equipped with a condenser, 16
g (0.1 mole) of bromobenzene, 9.8 g (50 mmole) of aminostilbene,
0.69 g (1.5% by mole) of tris(dibenzylideneacetone)dipalladium,
0.46 g (3% by mole) of tri-o-toluylphosphine, 7.2 g (75 mmole) of
sodium t-butoxide and 100 ml of dry toluene were placed under an
argon stream. The resulting mixture was stirred overnight under
heating at 100.degree. C. After the reaction was completed,
precipitated crystals were separated by filtration and washed with
100 ml of methanol. The obtained crude crystals were recrystallized
from 50 ml of ethyl acetate and 11 g (the yield: 80%) of
Intermediate Compound X of the object compound was obtained.
[0262] Synthesis of Intermediate Compound Y
[0263] In a 500 ml three-necked flask equipped with a condenser, 38
g (0.16 mole) of bromobenzene, 11 g (40 mmole) of Intermediate
Compound X, 0.55 g (1.5% by mole) of
tris(dibenzylideneacetone)-dipalladium, 0.37 g (3% by mole) of
tri-o-toluylphosphine, 5.8 g (60 mmole) of sodium t-butoxide and
300 ml of dry toluene were placed under an argon stream. The
resulting mixture was stirred overnight under heating at
120.degree. C. After the reaction was completed, precipitated
crystals were separated by filtration and washed with 100 ml of
methanol. The obtained crude crystals were recrystallized from 50
ml of ethyl acetate and 13 g (the yield: 75%) of Intermediate
Compound Y of the object compound was obtained.
[0264] Synthesis of Compound (123)
[0265] In a 300 ml three-necked flask equipped with a condenser,
0.97 g (40 mmole) of magnesium, a small piece of iodine and 50 ml
of tetrahydrofuran were placed under an argon stream. After the
resulting mixture was stirred at the room temperature for 30
minutes, 12 g (30 mole) of Intermediate Compound Y dissolved in 100
ml of tetrahydrofuran was added dropwise. After the addition was
completed, the reaction mixture was stirred under heating at
60.degree. C. for 1 hour and a Grignard reagent was prepared.
[0266] In a 500 ml three-necked flask equipped with a condenser,
3.4 g (10 mmole) of 9,10-dibromoanthracene, 0.4 g (5% by mole) of
dichlorobis(triphenylphosphine)palladium, 1 ml (1 mmole) of a 1 M
toluene solution of diisobutylaluminum hydride and 100 ml of
tetrahydrofuran were placed under an argon stream. To the obtained
mixture, the Grignard reagent prepared above was added dropwise at
the room temperature and the resulting mixture was refluxed
overnight. After the reaction was completed, the reaction liquid
was cooled with ice water. Precipitated crystals were separated by
filtration and washed with 50 ml of methanol and 50 ml of acetone,
successively, and 5.4 g of yellow powder was obtained. The obtained
powder was identified to be Compound (123) by the measurements in
accordance with NMR, IR and FD-MS (the yield: 50%).
[0267] The chemical structures of Intermediate Compounds and the
route of synthesis of Compound (123) are shown in the following.
##STR80##
SYNTHESIS EXAMPLE 21 (COMPOUND (124))
[0268] Synthesis of Compound (124)
[0269] In a 500 ml three-necked flask equipped with a condenser,
2.5 g (5 mmole) of 10,10'-dibromo-9,9'-bianthryl, 0.2 g (5% by
mole) of dichlorobis(triphenylphosphine)palladium, 0.5 ml (0.5
mmole) of a 1 M toluene solution of diisobutylaluminum, hydride and
100 ml of tetrahydrofuran were placed under an argon stream. To the
mixture, the Grignard reagent prepared in Synthesis Example 19 was
added dropwise at the room temperature and the resulting mixture
was refluxed overnight. After the reaction was completed, the
reaction liquid was cooled with ice water. Precipitated crystals
were separated by filtration and washed with 50 ml of methanol and
50 ml of acetone, successively, and 2.0 g of yellow powder was
obtained. The obtained powder was identified to be Compound (124)
by the measurements in accordance with NMR, IR and FD-MS (the
yield: 60%).
[0270] The route of synthesis of Compound (124) is shown in the
following. ##STR81##
SYNTHESIS EXAMPLE 22 (COMPOUND (125))
[0271] Synthesis of Compound (125)
[0272] In a 500 ml three-necked flask equipped with a condenser,
1.9 g (5 mmole) of 6,12-dibromochrysene, 0.2 g (5% by mole) of
dichlorobis(triphenylphosphine)palladium, 0.5 ml (0.5 mmole) of a 1
M toluene solution of diisobutylaluminum hydride and 100 ml of
tetrahydrofuran were placed under an argon stream. To the mixture,
the Grignard reagent prepared in Synthesis Example 19 was added
dropwise at the room temperature and the resulting mixture was
stirred under heating overnight. After the reaction was completed,
the reaction liquid was cooled with ice water. Precipitated
crystals were separated by filtration and washed with 50 ml of
methanol and 50 ml of acetone, successively, and 2.1 g of yellow
powder was obtained. The obtained powder was identified to be
Compound (125) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 60%).
[0273] The route of synthesis of Compound (125) is shown in the
following. ##STR82##
SYNTHESIS EXAMPLE 23 (COMPOUND (126))
[0274] Synthesis of Compound (126)
[0275] In a 500 ml three-necked flask equipped with a condenser,
1.9 g (5 mmole) of 5,12-dibromonaphthacene, 0.2 g (5% by mole) of
dichlorobis(triphenylphosphine)palladium, 0.5 ml (0.5 mmole) of a 1
M toluene solution of diisobutylaluminum hydride and 100 ml of
tetrahydrofuran were placed under an argon stream. To the mixture,
the Grignard reagent prepared in Synthesis Example 19 was added
dropwise at the room temperature and the resulting mixture was
stirred under heating overnight. After the reaction was completed,
the reaction liquid was cooled with ice water. Precipitated
crystals were separated by filtration and washed with 50 ml of
methanol and 50 ml of acetone, successively, and 2.1 g of yellow
powder was obtained. The obtained powder was identified to be
Compound (126) by the measurements in accordance with NMR, IR and
FD-MS (the yield: 60%).
[0276] The route of synthesis of Compound (126) is shown in the
following. ##STR83##
EXAMPLE 52
[0277] On a glass substrate having a size of 25 mm.times.75
mm.times.1.1 mm, a transparent anode of a film of indium tin oxide
having a thickness of 100 nm was formed and cleaned for 10 minutes
by using ultraviolet light and ozone in combination.
[0278] This glass substrate was placed into an apparatus for vacuum
vapor deposition (manufactured by NIPPON SHINKUU GIJUTU Co., Ltd.)
and the pressure was reduced to about 10.sup.-4 Pa. TPD74 described
above was vapor deposited at a speed of 0.2 nm/second and a layer
having a thickness of 60 nm was formed. Then, TPD78 having the
structure shown below was vapor deposited at a speed of 0.2
nm/second and a layer having a thickness of 20 nm was formed.
[0279] On the layer formed above, DPVDPAN having the structure
shown below and Compound (100) described above as the light
emitting material were simultaneously vapor deposited and a light
emitting layer having a thickness of 40 nm was formed. The speed of
vapor deposition of DPVDPAN was 0.4 nm/second and the speed of
vapor deposition of Compound (100) was 0.01 nm/second. On the layer
formed above, Alq described above was vapor deposited at a speed of
0.2 nm/second. Finally, aluminum and lithium were vapor deposited
simultaneously and a cathode having a thickness of 150 nm was
formed. Thus, an organic EL device was obtained. The speed of vapor
deposition of aluminum was 1 nm/second and the speed of vapor
deposition of lithium was 0.004 nm/second. ##STR84##
[0280] The properties of the obtained organic EL device were
evaluated. Luminance of emitted light at the voltage shown in Table
4 was measured and the efficiency of light emission was calculated.
The color of emitted light was observed. The organic EL device was
driven by a constant electric current under a nitrogen stream at an
initial luminance of emitted light of 500 (cd/m.sup.2) and the half
life time which was the time before the luminance decreases to 250
(cd/m.sup.2) was measured. The results are shown in Table 4.
EXAMPLES 53 TO 62
[0281] Organic EL devices were prepared in accordance with the same
procedures as those conducted in Example 52 except that the
compounds shown in Table 4 were used as the light emitting material
in place of Compound (100) and the properties were evaluated. The
results are shown in Table 4.
COMPARATIVE EXAMPLE 8
[0282] An organic EL devices was prepared in accordance with the
same procedures as those conducted in Example 52 except that the
diamine compound shown below was used as the light emitting
material in place of Compound (100) and the properties were
evaluated. The results are shown in Table 4. ##STR85##
TABLE-US-00004 TABLE 4 Luminance Efficiency of emitted of light
Half life Color Voltage light emission time of emitted (V)
(cd/m.sup.2) (lm/W) (hour) light Example 52 6.0 120 4.50 1800 green
53 6.0 240 3.90 2000 bluish green 54 6.0 130 4.60 1700 green 55 6.0
210 4.90 2500 green 56 7.0 230 4.00 1500 yellowish green 57 6.0 120
2.90 2100 blue 58 6.0 180 3.40 1800 bluish green 59 5.5 220 4.62
1700 blue 60 5.5 420 3.10 2200 bluish green 61 5.5 180 4.25 3100
blue 62 5.0 240 4.90 3200 bluish green Comparative Example 8 6.0
150 3.70 1200 green
[0283] As shown in Table 4, the organic EL devices of Examples 52
to 62 in which the compounds represented by general formulae [9]
and [10] of the present invention were used as the light emitting
material or the hole transporting material exhibited more excellent
luminance of emitted light and efficiencies of light emission and
longer lives in comparison with the organic EL device of
Comparative Example 8 in which the diamine compound was used.
SYNTHESIS EXAMPLE 24 (COMPOUND a)
[0284] Synthesis of Intermediate Compound A
[0285] In a 500 ml three-necked flask, 50 g (0.27 mole) of
p-bromobenzaldehyde, 50 g (0.22 mmole) of diethyl benzylphosphonate
and 200 ml of dimethylsulfoxide were placed under an argon stream.
To this was added 30 g (0.27 mole) of potassium t-butoxide in small
portions. The resulting mixture was stirred overnight at the room
temperature. After the reaction was completed, the reaction liquid
was poured into 500 ml of water and extracted with ethyl acetate.
The extract was dried with magnesium sulfate and concentrated in
vacuo using a rotary evaporator. The obtained crude crystals were
recrystallized from 100 ml of ethyl acetate and 46 g (the yield:
81%) of Intermediate Compound A was obtained.
[0286] Synthesis of Intermediate Compound B
[0287] Into a 300 ml three-necked flask equipped with a condenser,
10 g (38 mmole) of Intermediate Compound A, 14 g (150 mmole) of
aniline, 0.53 g (1.5% by mole) of
tris(dibenzylideneacetone)dipalladium, 0.35 g (3% by mole) of
tri-o-toluylphosphine, 7.4 g (77 mole) of sodium t-butoxide and 100
ml of dry toluene were placed under an argon stream. The resulting
mixture was stirred overnight under heating at 100.degree. C. After
the reaction was completed, precipitated crystals were separated by
filtration and washed with 100 ml of methanol. The obtained crude
crystals were recrystallized from 50 ml of ethyl acetate and 7.7 g
(the yield: 73%) of Intermediate Compound B was obtained.
[0288] Synthesis of Intermediate Compound C
[0289] In a 100 ml flask having an egg plant shape and equipped
with a condenser, 12.5 g (50 mmole) of 4-bromobenzyl bromide and
12.5 (75 mmole) of triethyl phosphite were placed. The resulting
mixture was stirred under heating at 100.degree. C. for 7 hours.
After the reaction was completed, triethyl phosphite in an excess
amount was removed by distillation in vacuo and 15.4 g of
Intermediate Compound C was obtained. Intermediate Compound C was
used in the following reaction without further purification.
[0290] Synthesis of Intermediate Compound D
[0291] In a 300 ml three-necked flask, 9.2 g (50 mmole) of
p-bromobenzaldehyde, 15.4 g (50 mmole) of Intermediate Compound C
and 100 ml of dimethylsulfoxide were placed under an argon stream.
To this was added 6.7 g (60 mmole) of potassium t-butoxide in small
portions and the resulting mixture was stirred overnight at the
room temperature. After the reaction was completed, the reaction
liquid was poured into 200 ml of water and extracted with ethyl
acetate. The extract was dried with magnesium sulfate and
concentrated in vacuo using a rotary evaporator. The obtained
crystals were washed with 100 ml of methanol and 13 g (the yield:
77%) of Intermediate compound D was obtained.
[0292] Synthesis of Compound a
[0293] In a 200 ml three-necked flask equipped with a condenser, 4
g (15 mmole) of Intermediate Compound B, 2 g (6 mmole) of
Intermediate Compound D, 0.16 g (3% by mole) of
tris(dibenzylideneacetone)dipalladium, 0.22 g (6% by mole) of
(S)-BINAP, 1.4 g (15 mmole) of sodium t-butoxide and 50 ml of dry
toluene were placed under an argon stream. The resulting mixture
was stirred overnight under heating at 100.degree. C. After the
reaction was completed, precipitated crystals were separated by
filtration, washed with methanol and dried by heating at 60.degree.
C. for one night. The obtained crude crystals were purified in
accordance with the column chromatography (silica gel,
hexane/toluene=8/2) and 1.4 g of yellow powder was obtained. The
obtained powder was identified to be Compound a by the measurements
in accordance with NMR, IR and FD-MS (the field desorption mass
spectroscopy) (the yield: 32%, in .sup.1H.sub.NMR (90 Hz): .delta.
7.0.about.7.4 ppm (42H, m)). The NMR chart of Compound a is shown
in FIG. 1.
[0294] The chemical reactions to obtain Compound a are shown in the
following: ##STR86##
SYNTHESIS EXAMPLE 25 (COMPOUND b)
[0295] Synthesis of Intermediate Compound E
[0296] In a 300 ml three-necked flask, 6 g (50 mmole) of
p-tolualdehyde, 15.4 g (50 mmole) of Intermediate Compound C and
100 ml of dimethylsulfoxide were placed under an argon stream. To
this was added 6.7 g (60 mmole) of potassium t-butoxide in small
portions and the resulting mixture was stirred overnight at the
room temperature. After the reaction was completed, the reaction
liquid was poured into 200 ml of water and extracted with ethyl
acetate. The extract was dried with magnesium sulfate and
concentrated in vacuo using a rotary evaporator. The obtained
crystals were washed with 100 ml of methanol and 9.2 g (the yield:
67%) of Intermediate Compound E was obtained.
[0297] Synthesis of Compound b
[0298] In a 200 ml three-necked flask equipped with a condenser, 4
g (15 mmole) of Intermediate Compound E, 2 g (6 mmole) of
N,N'-diphenylbenzidine, 0.16 g (3% by mole) of
tris(dibenzylideneacetone)-dipalladium, 0.22 g (6% by mole) of
(S)-BINAP, 1.4 g (15 mmole) of sodium t-butoxide and 50 ml of dry
toluene were placed under an argon stream. The resulting mixture
was stirred overnight under heating at 100.degree. C. After the
reaction was completed, precipitated crystals were separated by
filtration, washed with methanol and dried by heating at 60.degree.
C. for one night. The obtained crude crystals were purified in
accordance with the column chromatography (silica gel,
hexane/toluene=8/2) and 2.5 g of yellow powder was obtained. The
obtained powder was identified to be Compound b by the measurements
in accordance with NMR, IR and FD-MS (the yield: 58%, in
.sup.1H.sub.NMR (90 Hz): .delta. 7.0.about.7.4 ppm (40H, m),
.delta. 2.34 ppm (6H,s)). The NMR chart of Compound b is shown in
FIG. 2.
[0299] The chemical reactions to obtain Compound b are shown in the
following: ##STR87##
SYNTHESIS EXAMPLE 26 (COMPOUND c)
[0300] Synthesis of Compound c
[0301] In a 200 ml three-necked flask equipped with a condenser, 4
g (15 mmole) of Intermediate Compound B, 1.7 g (6 mmole) of
1,4-dibromonaphthalene, 0.16 g (3% by mole) of
tris(dibenzylideneacetone)-dipalladium, 0.22 g (6% by mole) of
(S)-BINAP, 1.4 g (15 mmole) of sodium t-butoxide and 50 ml of dry
toluene were placed under an argon stream. The resulting mixture
was stirred over night under heating at 100.degree. C. After the
reaction was completed, precipitated crystals were separated by
filtration, washed with methanol and dried by heating at 60.degree.
C. for one night. The obtained crude crystals were purified in
accordance with the column chromatography (silica gel,
hexane/toluene=8/2) and 2.0 g of yellow powder was obtained. The
obtained powder was identified to be Compound c by the measurements
in accordance with NMR, IR and FD-MS (the yield: 50%, in
.sup.1H.sub.NMR (90 Hz): .delta. 7.0.about.7.4 ppm (68H, m)).
[0302] The chemical reaction to obtain Compound c is shown in the
following: ##STR88##
SYNTHESIS EXAMPLE 27 (COMPOUND d)
[0303] Synthesis of Compound d
[0304] In a 200 ml three-necked flask equipped with a condenser, 4
g (15 mmole) of Intermediate Compound B, 2 g (6 mmole) of
9,10-dibromoanthracene, 0.16 g (3% by mole) of
tris(dibenzylideneacetone)-dipalladium, 0.07 g (6% by mole) of
tri-t-butylphosphine, 1.4 g (15 mmole) of sodium t-butoxide and 50
ml of dry toluene were placed under an argon stream. The resulting
mixture was stirred overnight under heating at 100.degree. C. After
the reaction was completed, precipitated crystals were separated by
filtration, washed with methanol and dried by heating at 60.degree.
C. for one night. The obtained crude crystals were purified in
accordance with the column chromatography (silica gel,
hexane/toluene=8/2) and 1.9 g of yellow powder was obtained. The
obtained powder was identified to be Compound d by the measurements
in accordance with NMR, IR and FD-MS (the yield: 44%, in
.sup.1H.sub.NMR (90 Hz): .delta. 7.0.about.7.4 ppm (40H, m)).
[0305] The chemical reaction to obtain Compound d is shown in the
following: ##STR89##
SYNTHESIS EXAMPLE 28 (COMPOUND e)
[0306] Synthesis of Intermediate Compound E
[0307] In a 300 ml three-necked flask, 10.4 g (50 mmole) of
trans-4-stilbenealdehyde, 15.4 g (50 mmole) of Intermediate
Compound C and 100 ml of dimethylsulfoxide were placed under an
argon stream. To this was added 6.7 g (60 mmole) of potassium
t-butoxide in small portions and the resulting mixture was stirred
overnight at the room temperature. After the reaction was
completed, the reaction liquid was poured into 200 ml of water and
extracted with ethyl acetate. The extract was dried with magnesium
sulfate and concentrated in vacuo using a rotary evaporator. The
obtained crystals were washed with 100 ml of methanol and 12.5 g
(the yield: 69%) of Intermediate Compound F was obtained.
[0308] Synthesis of Compound e
[0309] In a 200 ml three-necked flask equipped with a condenser,
5.4 g (15 mmole) of Intermediate Compound F, 2 g (6 mmole) of
N,N'-diphenylbenzidine, 0.16 g (3% by mole) of
tris(dibenzylideneacetone)-dipalladium, 0.11 g (6% by mole) of
tri-o-toluylphosphine, 1.4 g (15 mmole) of sodium t-butoxide and 50
ml of dry toluene were placed under an argon stream. The resulting
mixture was stirred overnight under heating at 100.degree. C. After
the reaction was completed, precipitated crystals were separated by
filtration, washed with methanol and dried by heating at 60.degree.
C. for one night. The obtained crude crystals were purified in
accordance with the column chromatography (silica gel,
hexane/toluene=6/4) and 1.0 g of yellow powder was obtained. The
obtained powder was identified to be Compound e by the measurements
in accordance with NMR, IR and FD-MS (the yield: 19%, in
.sup.1H.sub.NMR (90 Hz): .delta. 7.0.about.7.5 ppm (52H, m)). The
NMR chart of Compound e is shown in FIG. 3.
[0310] The chemical reactions to obtain Compound e are shown in the
following: ##STR90## Synthesis of Compound f
[0311] In a 200 ml three-necked flask equipped with a condenser,
7.8 g (30 mmole) of Intermediate Compound A, 1.7 g (6 mmole) of
4,4'-diaminostilbene carbon dioxide, 0.16 g (3% by mole) of
tris(dibenzylideneacetone)dipalladium, 0.22 g (6% by mole) of
(S)-BINAP, 9.6 g (0.1 mole) of sodium t-butoxide and 50 ml of dry
toluene were placed under an argon stream. The resulting mixture
was stirred overnight under heating at 100.degree. C. After the
reaction was completed, precipitated crystals were separated by
filtration, washed with methanol and dried by heating at 60.degree.
C. for one night. The obtained crude crystals were purified in
accordance with the column chromatography (silica gel,
hexane/toluene=6/4) and 2.0 g of yellow powder was obtained. The
obtained powder was identified to be Compound f by the measurements
in accordance with NMR, IR and FD-MS (the yield: 36%, in
.sup.1H.sub.NMR (90 Hz): .delta. 7.0.about.7.5 ppm (54H, m)).
[0312] The chemical reaction to obtain Compound f is shown in the
following: ##STR91##
EXAMPLE 63
[0313] On a cleaned glass plate having an ITO electrode, TPD74
described above was vacuum vapor deposited as the hole injecting
material and a layer having a thickness of 60 nm was formed.
[0314] Then, NPD described above was vacuum vapor deposited as the
hole transporting material and a layer having a thickness of 20 nm
was formed.
[0315] Subsequently, as the light emitting materials,
4,4'-bis(2,2-diphenylvinyl)biphenyl (DPVBi) which is a stilbene
derivative and Compound a described above were simultaneously vapor
deposited and a layer having a content of Compound a of 2% by
weight and a thickness of 40 nm was formed. Compound a works as a
fluorescent dopant or the light emitting center. On the layer
formed above, Alq described above was vapor deposited as the
electron injecting material and a layer having a thickness of 20 nm
was formed. After lithium fluoride was vapor deposited and a layer
having a thickness of 0.5 nm was formed, aluminum was vapor
deposited and a layer having a thickness of 100 nm was formed.
Thus, an electrode was formed and an organic EL device was
obtained. The layers were vapor deposited in a vacuum of 10.sup.-6
Torr while the substrate was kept at the room temperature. The
device exhibited a luminance of emitted light of 100 (cd/m.sup.2)
and an efficiency of light emission of 2.1 (lm/W) under application
of a direct current voltage of 6 V. The color coordinate was
(0.146, 0.140) and blue light of a high purity could be emitted.
When the organic EL device was driven by a constant electric
current at an initial luminance of emitted light of 200
(cd/m.sup.2), the half life time was as long as 2,000 hours. The
properties of light emission are shown in Table 5.
[0316] The energy gap of Compound a was 2.78 eV and the energy gap
of DPVBi was 3.0 eV.
EXAMPLE 64
[0317] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 63 except that
Compound b was used as the dopant or the light emitting center. The
device exhibited a luminance of emitted light of 110 (cd/m.sup.2)
and an efficiency of light emission of 1.3 (lm/W) under application
of a direct current voltage of 6 V. The color coordinate was
(0.152, 0.163) and blue light of a high purity could be emitted.
When the organic EL device was driven by a constant electric
current at an initial luminance of emitted light of 200
(cd/m.sup.2), the half life time was as long as 1,500 hours. The
properties of light emission are shown in Table 5.
[0318] The energy gap of Compound b was 2.90 eV and the energy gap
of DPVBi was 3.0 eV.
EXAMPLE 65
[0319] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 63 except that
Compound c was used as the dopant or the light emitting center. The
device exhibited a luminance of emitted light of 130 (cd/m.sup.2)
and an efficiency of light emission of 2.1 (lm/W) under application
of a direct current voltage of 6 V. The color coordinate was
(0.162, 0.181) and blue light of a high purity could be emitted.
When the organic EL device was driven by a constant electric
current at an initial luminance of emitted light of 200
(cd/m.sup.2), the half life time was as long as 2,800 hours. The
properties of light emission are shown in Table 5.
[0320] The energy gap of Compound b was 2.83 eV and the energy gap
of DPVBi was 3.0 eV.
EXAMPLE 66
[0321] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 63 except that
Compound d was used as the dopant or the light emitting center. The
device exhibited a luminance of emitted light of 300 (cd/m.sup.2)
and an efficiency of light emission of 4.6 (lm/W) under application
of a direct current voltage of 6 V. Light of green color could be
emitted with a high efficiency. When the organic EL device was
driven by a constant electric current at an initial luminance of
emitted light of 200 (cd/m.sup.2), the half life time was as long
as 3,400 hours. The properties of light emission are shown in Table
5.
[0322] The energy gap of Compound d was 2.78 eV and the energy gap
of DPVBi was 3.0 eV.
COMPARATIVE EXAMPLE 9
[0323] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 63 except that the
following compound (TPD): ##STR92## was used as the dopant or the
light emitting center. The device exhibited a luminance of emitted
light of 60 (cd/m.sup.2) and an efficiency of light emission of 0.7
(lm/W) under application of a direct current voltage of 5 V.
Sufficient properties could not be obtained. TPD did not work as
the light emitting center and light emitted from DPVTP was
obtained. When the organic EL device was driven by a constant
electric current at an initial luminance of emitted light of 200
(cd/m.sup.2), the half life time was as short as 100 hours. The
properties of light emission are shown in Table 5.
[0324] The energy gap of TPD was 3.10 eV and the energy gap of
DPVBi was 3.0 eV.
COMPARATIVE EXAMPLE 10
[0325] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 63 except that
Compound a described above was used as the dopant or the light
emitting material and the compound Alq was used as the light
emitting material. The device exhibited a luminance of emitted
light of 210 (cd/m.sup.2) and an efficiency of light emission of
1.3 (lm/W) under application of a direct current voltage of 6 V.
However, light of pink color from Alq alone was obtained. When the
organic EL device was driven by a constant electric current at an
initial luminance of emitted light of 200 (cd/m.sup.2), the half
life time was as short as 200 hours. The properties of light
emission are shown in Table 5. Compound a did not work as the light
emitting center.
[0326] The energy gap of Compound a was 2.95 eV and the energy gap
of Alq was 2.7 eV.
COMPARATIVE EXAMPLE 11
[0327] An organic EL device was prepared in accordance with the
same procedures as those conducted in Example 63 except that no
dopant or light emitting material was used and Compound c described
above was used as the single light emitting material. The device
exhibited luminance of emitted light of 40 (cd/m.sup.2) and an
efficiency of light emission of 0.9 (lm/W) under application of a
direct current voltage of 6 V. Sufficient properties could not be
obtained. When the organic EL device was driven by a constant
electric current at an initial luminance of emitted light of 200
(cd/m.sup.2), the half life time was as short as 180 hours. The
properties of light emission are shown in Table 5.
[0328] The properties of light emission obtained above are shown in
Table 5. TABLE-US-00005 TABLE 4 Dopant or Luminance Efficiency
Color light Light Applied of emitted of light of Half life emitting
emitting voltage light emission emitted time center material (V)
(cd/m.sup.2) (lm/W) light (hour) Example 63 Compound a DPVBi 6 100
2.1 blue 2000 64 Compound b DPVBi 6 110 1.3 blue 1500 65 Compound c
DPVBi 6 130 2.1 blue 2800 66 Compound d DPVBi 6 300 4.6 green 3400
Comparative Example 9 TPD DPVBi 5 60 0.7 blue 100 10 Compound a Alq
6 210 1.3 green 200 11 none Compound c 6 40 0.9 blue 180
[0329] As shown in Table 5, the organic EL devices of Examples 63
to 66 in which a small amount (1 to 20% by weight) of a compound
represented by general formula [1] was added to the host material
as the dopant or the light emitting center exhibited higher
efficiencies of light emission and much longer lives in comparison
with the organic EL devices of Comparative Examples 9 to 11.
INDUSTRIAL APPLICABILITY
[0330] The organic EL devices of the present invention in which the
materials for organic EL devices represented by general formulae
[1], [3] to [6] and [9] to [10] described above are used as the
light emitting material, the hole injecting material, the hole
transporting material or the doping material exhibit luminances of
light emission sufficient for practical use and high efficiencies
of light emission under application of a low voltage, have long
lives because the decrease in the properties after use for a long
time is suppressed and show no deterioration in the properties in
the environment of high temperatures due to excellent heat
resistance.
[0331] The organic EL devices described above in which the
materials for organic EL devices represented by general formulae
[7] and [8] are used as the light emitting material, the hole
injecting material, the hole transporting material or the doping
material exhibit, in the region of yellow color and orange to red
color, luminances of light emission sufficient for practical use
and high efficiencies of light emission under application of a low
voltage and have long life times because the decrease in the
properties after use for a long time is suppressed.
[0332] The organic EL devices in which the material for organic EL
devices comprising the compound represented by general formula [11]
of the present invention or the novel compound represented by
general formula [11'] of the present invention is used as the
dopant or the light emitting center exhibit luminances of emitted
light sufficient for practical use under application of a low
voltage and high efficiencies of light emission and have long lives
because the decrease in the properties after use for a long time is
suppressed.
[0333] By producing materials for organic EL devices in accordance
with the process of the present invention, materials for organic EL
devices exhibiting a high efficiency of light emission, having a
long life, showing high activity and containing little impurities
can be produced in a high yield.
* * * * *