U.S. patent application number 13/611991 was filed with the patent office on 2013-01-03 for polymer compound and polymer light emitting device using the same.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. Invention is credited to Hidenobu KAKIMOTO, Takanobu NOGUCHI, Tomoyuki SUZUKI.
Application Number | 20130002989 13/611991 |
Document ID | / |
Family ID | 36615017 |
Filed Date | 2013-01-03 |
United States Patent
Application |
20130002989 |
Kind Code |
A1 |
NOGUCHI; Takanobu ; et
al. |
January 3, 2013 |
POLYMER COMPOUND AND POLYMER LIGHT EMITTING DEVICE USING THE
SAME
Abstract
A polymer compound containing a structure of the following
formula (B): --Ar-- (A) (wherein, Ar represents an arylene group,
divalent heterocyclic group, divalent aromatic amine group or
divalent group having a metal complex structure.) ##STR00001##
(wherein, A ring and B ring represent each independently an
aromatic ring optionally having a substituent. X.sub.1 represents
--C(.dbd.O)--, --S(.dbd.O)--, --S(.dbd.O).sub.2--,
--P(.dbd.O)(R.sub.1)--, --C(R.sub.1)(R.sub.2)--,
--C(R.sub.2)(R.sub.2)--, --B(R.sub.1)--, --N(R.sub.1)-- or
--Si(R.sub.1)(R.sub.1)--. R* represents a hydrogen atom or
monovalent or divalent group, R.sub.1 represents a hydrogen atom or
monovalent group, and R.sub.2 represents a monovalent group having
a hetero atom. When R.sub.1 and R.sub.2 are present each in plural
number, they may be the same or different.).
Inventors: |
NOGUCHI; Takanobu;
(Tsukuba-shi, JP) ; KAKIMOTO; Hidenobu;
(Tsukuba-shi, JP) ; SUZUKI; Tomoyuki;
(Nishitokyo-shi, JP) |
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED
Tokyo
JP
|
Family ID: |
36615017 |
Appl. No.: |
13/611991 |
Filed: |
September 12, 2012 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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11722231 |
Jun 20, 2007 |
8293380 |
|
|
PCT/JP2005/024211 |
Dec 26, 2005 |
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13611991 |
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Current U.S.
Class: |
349/69 ;
252/301.35; 252/500; 257/40; 257/E51.026; 524/592; 528/220 |
Current CPC
Class: |
H01L 51/0035 20130101;
C08G 61/122 20130101; H01L 51/0085 20130101; H01L 51/5048 20130101;
H01L 51/0039 20130101; C08G 73/0688 20130101; H01L 51/5012
20130101; G02F 2202/022 20130101; C09D 11/102 20130101; G02F
1/133603 20130101; H01L 51/0043 20130101 |
Class at
Publication: |
349/69 ; 528/220;
524/592; 252/500; 252/301.35; 257/40; 257/E51.026 |
International
Class: |
C08G 73/06 20060101
C08G073/06; C09D 11/00 20060101 C09D011/00; H01L 51/54 20060101
H01L051/54; C09K 11/06 20060101 C09K011/06; G02F 1/13357 20060101
G02F001/13357; C09D 179/04 20060101 C09D179/04; H01B 1/12 20060101
H01B001/12 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 27, 2004 |
JP |
2004-375924 |
Jan 28, 2005 |
JP |
2005-020961 |
Claims
1. A polymer compound having one or more repeating units of the
following formula (A) and containing further a structure of the
following formula (B): --Ar-- (A) wherein, Ar represents an arylene
group, divalent heterocyclic group, divalent aromatic amine group
or divalent group having a metal complex structure ##STR00070##
wherein, A ring and B ring represent each independently an aromatic
ring optionally having a substituent, X represents --C(.dbd.O)--,
--S(.dbd.O)--, --S(.dbd.O).sub.2--, --P(.dbd.O)(R.sub.1)--,
--C(R.sub.1)(R.sub.2)--, --C(R.sub.2)(R.sub.2)--, --B(R.sub.1)--,
--N(R.sub.1)-- or --Si(R.sub.1)(R.sub.1)--, R* represents a
hydrogen atom or monovalent or divalent group, R.sub.1 represents a
hydrogen atom or monovalent group, and R.sub.2 represents a
monovalent group having a hetero atom, and when R.sub.1 and R.sub.2
are present each in plural number, they may be the same or
different, wherein the polymer compound has a structure of the
following formula (1): ##STR00071## wherein, A.sub.1 represents a
hydrogen atom, alkyl group, aryl group, arylalkyl group,
aryloxyalkyl group, monovalent heterocyclic group or divalent
group, R represents a hydrogen atom, alkyl group, alkoxy group,
alkylthio group, alkylsilyl group, alkylamino group, aryl group,
aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl
group, arylalkynyl group, arylamino group, monovalent heterocyclic
group or cyano group, Z*s represent each independently a direct
bond or R, J and K represent each independently an integer from 0
to 3, J1 and K1 represent each independently 0 or 1, and when a
plurality of Rs are present, they may be the same or different, and
wherein the polymer compound contains a repeating unit of the
following formula (3): ##STR00072## wherein A.sub.2s represent each
independently a group of the following formula (4):
*--(Ar.sub.1)j.sub.1-(X)k.sub.1-(Ar.sub.2)p.sub.1-(Y)q.sub.1- (4)
wherein, Ar.sub.1 and Ar.sub.2 represent each independently an
arylene group, divalent heterocyclic group or divalent aromatic
amine group, X represents --R.sub.7--, --O--R.sub.7--,
--R.sub.7--O--, --R.sub.7--C(O)O--, --R.sub.7--OC(O)--,
--R.sub.7--N(R.sub.20)--, --O--, --S--, --C(O)O-- or --C(O)--, Y
represents --C(R.sub.20).dbd.C(R.sub.20)-- or --C.ident.C--,
j.sub.1, k.sub.1, p.sub.1 and q.sub.1 are each independently 0 or
1, R.sub.7 represents an alkylene group, R.sub.20 represents a
hydrogen atom, alkyl group, aryl group, monovalent heterocyclic
group or cyano group, and * represents a site to be connected to N,
n.sub.1 and n.sub.2 represent each independently 0 or 1, and R is
as described above, and a plurality of Rs may be the same or
different.
2. The polymer compound according to claim 1, further containing a
repeating unit of the following formula (31):
--Ar.sub.4--(Z'').sub.t-- (31) wherein, Ar.sub.4 represents an
arylene group, divalent heterocyclic group or divalent aromatic
amine group, Z' represents --CR.sub.8.dbd.CR.sub.9-- or
--C.ident.C--, R.sub.8 and R.sub.9 represent each independently a
hydrogen atom, alkyl group, aryl group, monovalent heterocyclic
group or cyano group, and t represents 0 or 1.
3. The polymer compound according to claim 1, wherein n.sub.1 and
n.sub.2 are both 0 in the repeating unit of said formula (3).
4. A composition comprising at least one material selected from the
group consisting of hole transporting materials, electron
transporting materials and light emitting materials and at least
one of the polymer compound according to claim 1.
5. An ink composition comprising the polymer compound according to
claim 1.
6. A thin film comprising the polymer compound according to claim
1.
7. An electrically conductive thin film comprising the polymer
compound according to claim 1.
8. An organic semiconductor thin film comprising the polymer
compound according to claim 1.
9. An organic transistor having the organic semiconductor thin film
according to claim 1.
10. A polymer light emitting device having an organic layer
containing the polymer compound according to claim 1 between
electrodes composed of an anode and a cathode.
11. The polymer light emitting device according to claim 10 herein
said organic layer is a light emitting layer.
12. The polymer light emitting device according to claim 11 wherein
said light emitting layer contains further a hole transporting
material, electron transporting material or light emitting
material.
13. The polymer light emitting device according to claim 10 wherein
a light emitting layer and a charge transporting layer are present
between the electrodes composed of an anode and a cathode and the
charge transporting layer contains a polymer compound one or more
repeating units of the following formula (A) and containing further
a structure of the following formula (B): --Ar-- (A) wherein, Ar
represents an arylene group, divalent heterocyclic group, divalent
aromatic amine group or divalent group having a metal complex
structure, ##STR00073## wherein, A ring and B ring represent each
independently an aromatic ring optionally having a substituent, X
represents --C(.dbd.O)--, --S(.dbd.O)--, --S(.dbd.O).sub.2--,
--P(.dbd.O)(R.sub.1)--, --C(R.sub.1)(R.sub.2)--,
--C(R.sub.2)(R.sub.2)--, --B(R.sub.1)--, --N(R.sub.1)-- or
--Si(R.sub.1)(R.sub.1)--, R* represents a hydrogen atom or
monovalent or divalent group, R.sub.1 represents a hydrogen atom or
monovalent group, and R.sub.2 represents a monovalent group having
a hetero atom, and when R.sub.1 and R.sub.2 are present each in
plural number, they may be the same or different.
14. The polymer light emitting device according to claim 10 wherein
a light emitting layer and a charge transporting layer are present
between the electrodes composed of an anode and a cathode, a charge
injection layer is present between the charge transporting layer
and the electrode and the charge injection layer contains a polymer
compound one or more repeating units of the following formula (A)
and containing further a structure of the following formula (B):
--Ar-- (A) wherein, Ar represents an arylene group, divalent
heterocyclic group, divalent aromatic amine group or divalent group
having a metal complex structure, ##STR00074## wherein, A ring and
B ring represent each independently an aromatic ring optionally
having a substituent, X represents --C(.dbd.O)--, --S(.dbd.O)--,
--S(.dbd.O).sub.2--, --P(.dbd.O)(R.sub.1)--,
--C(R.sub.1)(R.sub.2)--, --C(R.sub.2)(R.sub.2)--, --B(R.sub.1)--,
--N(R.sub.1)-- or --Si(R.sub.1)(R.sub.1)--, R* represents a
hydrogen atom or monovalent or divalent group, R.sub.1 represents a
hydrogen atom or monovalent group, and R.sub.2 represents a
monovalent group having a hetero atom, and when R.sub.1 and R.sub.2
are present each in plural number, they may be the same or
different.
15. A sheet light source using the polymer light emitting device
according to claim 10.
16. A segment display using the polymer light emitting device
according to claim 10.
17. A dot matrix display using the polymer light emitting device
according to claim 10.
18. A liquid crystal display using as backlight the polymer light
emitting device according to claim 10.
Description
[0001] This is a Continuation of application Ser. No. 11/722,231
filed Jun. 20, 2007, which is a 371 of PCT Application No.
PCT/JP2005/024211 filed Dec. 26, 2005, which claims benefit to
Japanese Patent Application No. 2004-375924 filed Dec. 27, 2004 and
Japanese Patent Application No. 2005-020961 filed Jan. 28, 2005.
The above-noted applications are incorporated herein by reference
in their entirety.
TECHNOLOGICAL FIELD
[0002] The present invention relates to a polymer compound and a
polymer light emitting device (hereinafter, referred to as polymer
LED in some cases) using the polymer compound.
BACKGROUND TECHNOLOGY
[0003] Light emitting materials of higher molecular weight are
soluble insolvents and capable of forming alight emitting layer in
a light emitting device by an application method, differing from
light emitting materials of lower molecular weight, thus, have been
investigated variously, and for example, there are known
polyphenylenevinylene derivatives, polyfluorene derivatives,
polyphenylene derivatives and the like.
DISCLOSURE OF THE INVENTION
[0004] The present invention has an object of providing a novel
polymer compound useful as a light emitting material, and a polymer
light emitting device using this polymer compound.
[0005] That is, the present invention provides the following
polymer compounds [1] to [3].
[0006] [1] A polymer compound having one or more repeating units of
the following formula (A) and containing further a structure of the
following formula (B):
--Ar-- (A)
(wherein, Ar represents an arylene group, divalent heterocyclic
group, divalent aromatic amine group or divalent group having a
metal complex structure.)
##STR00002##
(wherein, A ring and B ring represent each independently an
aromatic ring optionally having a substituent. X.sub.1 represents
--C(.dbd.O)--, --S(.dbd.O)--, --S(.dbd.O).sub.2--,
--P(.dbd.O)(R.sub.1)--, --C(R.sub.1)(R.sub.2)--,
--C(R.sub.2)(R.sub.2)--, --B(R.sub.1)--, --N(R.sub.1)-- or
--Si(R.sub.1)(R.sub.1)--. R* represents a hydrogen atom or
monovalent or divalent group, R.sub.1 represents a hydrogen atom or
monovalent group, and R.sub.2 represents a monovalent group having
a hetero atom. When R.sub.1 and R.sub.2 are present each in plural
number, they may be the same or different.).
[0007] [2] The above-described polymer compound, containing a
repeating unit of the following formula (2):
##STR00003##
(wherein, Z represents --CR.sub.3.dbd.CR.sub.4-- or --C.ident.C--.
R.sub.3 and R.sub.4 represent each independently a hydrogen atom,
alkyl group, aryl group, monovalent heterocyclic group or cyano
group. j and k represent each independently an integer of 0 to 3. m
represents 0 or 1. A.sub.1 represents a hydrogen atom, alkyl group,
aryl group, arylalkyl group, aryloxyalkyl group, monovalent
heterocyclic group or divalent group. R represents a hydrogen atom,
alkyl group, alkoxy group, alkylthio group, alkylsilyl group,
alkylamino group, aryl group, aryloxy group, arylalkyl group,
arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino
group, monovalent heterocyclic group or cyano group. j and k
represent each independently an integer from 0 to 3. When a
plurality of Rs are present, they may be the same or
different.).
[0008] [3] The above-described polymer compound, containing a
repeating unit of the following formula (3):
##STR00004##
(wherein A.sub.2s represent each independently a group of the
following formula (4):
*--(Ar.sub.1)j.sub.1-(X)k.sub.1-(Ar.sub.2)p.sub.1-(Y)q.sub.1-
(4)
(wherein, Ar.sub.1 and Ar.sub.2 represent each independently an
arylene group, divalent heterocyclic group or divalent aromatic
amine group, X represents --R.sub.7--, --O--R.sub.7--,
--R.sub.7--O--, --R.sub.7--C(O)O--, --R.sub.7--OC(O)--,
--R.sub.7--N(R.sub.20)--, --O--, --S--, --C(O)O-- or --C(O)--, Y
represents --C(R.sub.20).dbd.C(R.sub.20)-- or --C.ident.C--,
j.sub.1, k.sub.1, p.sub.1 and q.sub.1 are each independently 0 or
1, R.sub.7 represents an alkylene group, R.sub.20 represents a
hydrogen atom, alkyl group, aryl group, monovalent heterocyclic
group or cyano group, and represents a site to be connected to N.),
n.sub.1 and n.sub.2 represent each independently 0 or 1, and R is
as described above. A plurality of Rs may be the same or
different.).
BEST MODES FOR CARRYING OUT THE INVENTION
[0009] The polymer compound of the present invention contains one
or more repeating units of the above-described formula (A) and
contains further a structure of the above-described formula
(B).
[0010] The case of containing a structure of the above-described
formula (B) in a polymer compound includes cases of containing a
structure of the above-described formula (B) at any of the main
chain, side chain and end of a polymer compound, or cases of
containing a structure containing the above-described formula (B)
as a partial structure at any of the main chain, side chain and end
of a polymer compound.
[0011] As the structure containing the above-described formula (B)
as a partial structure, for example, the following structure is
mentioned.
##STR00005##
(wherein, A ring, X.sub.1 and R* represent the same meanings as
described above. B' ring and C ring represent each independently an
aromatic ring optionally having a substituent.).
[0012] There are a case of containing one structure of the
above-described formula (B) in the main chain in a polymer
compound, a case of containing the structure as a unit in the main
chain of a repeating polymer compound, a case of containing the
structure in the side chain of a polymer compound, and a case of
containing the structure at the end of a polymer compound.
[0013] The structure of the above-described formula (B) is, when
contained as a repeating unit in the main chain in a polymer
compound, contained in an amount of preferably 0.1 mol % or more,
more preferably 0.1 mol % or more and 90 mol % or less based on the
total amount of all repeating units in the polymer compound of the
present invention, from the standpoint of light emitting
efficiency.
[0014] When the structure of the above-described formula (B) is
represented by the following formula (B-2), the structure is
present at the side chain or end of a polymer compound. In this
case, the structure of the above-described formula (B) may be or
may not be contained in a repeating unit of a polymer compound.
##STR00006##
[0015] When the structure of the above-described formula (B) is
contained in the main chain of a polymer compound, branching may
exist at a site in the above-described formula (B).
[0016] In the above-described formula (B), A ring and B ring
represent each independently an aromatic ring optionally having a
substituent. The aromatic ring includes aromatic hydrocarbon rings
such as a benzene ring, naphthalene ring, anthracene ring,
phenanthrene ring, pyrene ring, perylene ring, tetracene ring,
pentacene ring and the like; and heteroaromatic rings such as a
pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring,
quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline
ring, acridine ring, phenanthroline ring, thiophene ring,
benzothiophene ring, dibenzothiophene ring, thiophene oxide ring,
benzothiophene oxide ring, dibenzothiophenen oxide ring, furan
ring, benzofuran ring, pyrrole ring, indole ring, dibenzopyrrole
ring, silole ring, benzosilole ring, dibenzosilole ring, borole
ring, benzoborole ring, dibenzoborole ring and the like. From the
standpoint of heat resistance, fluorescence intensity, device
properties and the like, preferable are aromatic hydrocarbon rings,
and among others, a benzene ring, naphthalene ring, anthracene ring
and phenanthrene ring are preferable. As specific examples of B'
ring and C ring in the above-described examples of a structure
containing the above-described formula (B), the same examples as
for the above-mentioned A ring and B ring are mentioned.
[0017] As the combination of A ring and B ring, preferably
mentioned are combinations of benzene ring and benzene ring,
benzene ring and naphthalene ring, benzene ring and anthracene
ring, benzene ring and phenanthrene ring, naphthalene ring and
anthracene ring, naphthalene ring and phenanthrene ring, and
anthracene ring and phenanthrene ring, and more preferable is a
combination of benzene ring and benzene ring.
[0018] R* in the above-described formula (B) represents a hydrogen
atom; a monovalent group such as an alkyl group, aryl group,
arylalkyl group, aryloxyalkyl group, monovalent heterocyclic group
and the like; or a divalent group.
[0019] From the standpoint of light emitting efficiency, preferable
is an alkyl group, aryl group, arylalkyl group, aryloxyalkyl group
or monovalent heterocyclic group. From the standpoint of
solubility, preferable is an alkyl group, arylalkyl group or
aryloxyalkyl group.
[0020] Here, the alkyl group may be any of linear, branched or
cyclic, and has a carbon number of usually about 1 to 20, and as
specific examples thereof, a methyl group, ethyl group, propyl
group, i-propyl group, butyl group, i-butyl group, t-butyl group,
pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl
group, 2-ethylhexyl group, nonyl group, decyl group,
3,7-dimethyloctyl group, lauryl group and the like are mentioned,
and preferable are a methyl group, ethyl group, propyl group, butyl
group, pentyl group, hexyl group, octyl group, 2-ethylhexyl group,
decyl group and 3,7-dimethyloctyl group.
[0021] The aryl group has a carbon number of usually about 6 to 60,
and as specific examples thereof, a phenyl group, C.sub.1 to
C.sub.12 alkoxyphenyl groups (C.sub.1 to C.sub.12 means a carbon
number of 1 to 12. Applicable also in the later descriptions),
C.sub.1 to C.sub.12 alkylphenyl groups, 1-naphthyl group,
2-naphthyl group and the like are exemplified, and preferable are a
phenyl group, C.sub.1 to C.sub.12 alkoxyphenyl groups and C.sub.1
to C.sub.12 alkylphenyl groups.
[0022] The arylalkyl group has a carbon number of usually about 7
to 60, and as specific examples thereof, phenyl-C.sub.1 to C.sub.12
alkyl groups, C.sub.1 to C.sub.12 alkoxyphenyl-C.sub.1 to C.sub.12
alkyl groups, C.sub.1 to C.sub.12 alkylphenyl-C.sub.1 to C.sub.12
alkyl groups, 1-naphthyl-C.sub.1 to C.sub.12 alkyl groups,
2-naphthyl-C.sub.1 to C.sub.12 alkyl groups and the like are
exemplified, and preferable are C.sub.1 to C.sub.12
alkoxyphenyl-C.sub.1 to C.sub.12 alkyl groups and C.sub.1 to
C.sub.12 alkylphenyl-C.sub.1 to C.sub.12 alkyl groups.
[0023] The aryloxyalkyl group has a carbon number of usually about
7 to 60, and as specific examples thereof, phenyloxy-C.sub.1 to
C.sub.12 alkyl groups, C.sub.1 to C.sub.12 alkoxyphenyloxy-C.sub.1
to C.sub.12 alkyl groups, C.sub.1 to C.sub.12
alkylphenyloxy-C.sub.1 to C.sub.12 alkyl groups,
1-naphthyloxy-C.sub.1 to C.sub.12 alkyl groups,
2-naphthyloxy-C.sub.1 to C.sub.12 alkyl groups and the like are
exemplified, and preferable are C.sub.1 to C.sub.12
alkoxyphenyloxy-C.sub.1 to C.sub.12 alkyl groups and C.sub.1 to
C.sub.12 alkylphenyloxy-C.sub.1 to C.sub.12 alkyl groups.
[0024] The monovalent heterocyclic group means an atom group
remaining after removal of one hydrogen atom from a heterocyclic
compound. The monovalent heterocyclic group has a carbon number of
usually about 4 to 60, and specifically, a thienyl group, C.sub.1
to C.sub.12 alkylthienyl groups, pyrrolyl group, furyl group,
pyridyl group, C.sub.1 to C.sub.12 alkylpyridyl groups and the like
are exemplified, and preferable are a thienyl group, C.sub.1 to
C.sub.12 alkylthienyl groups, pyridyl group and C.sub.1 to C.sub.12
alkylpyridyl groups.
[0025] In the polymer compound of the present invention, it is
preferable from the standpoint of light emitting efficiency that
the light emitting wavelength of a polymer compound composed of a
structure of the above-mentioned formula (B) is longer by 30 nm or
more than the light emitting wavelength of a polymer compound
composed of a structure of the above-mentioned formula (A).
[0026] In the formula, X.sub.1 represents --C(.dbd.O)--,
--S(.dbd.O)--, --S(.dbd.O).sub.2--, --P(.dbd.O)(R.sub.1)--,
--C(R.sub.1)(R.sub.2)--, --C(R.sub.2)(R.sub.2)--, --B(R.sub.1)--,
--N(R.sub.1)-- or --Si(R.sub.1)(R.sub.1)--. Among them,
--C(.dbd.O)-- is preferable. Here, R.sub.1s represent each
independently a hydrogen atom; a monovalent group such as an alkyl
group, aryl group, arylalkyl group, aryloxyalkyl group, monovalent
heterocyclic group and the like. R.sub.2s represent each
independently a monovalent group having a hetero atom (specifically
mentioned are alkoxy groups, alkylamino groups, alkylthio groups,
alkyloxyalkyl groups, alkylaminoalkyl groups, alkylthioalkyl
groups, aryloxy groups, aryloxyalkyl groups, alkyl groups in which
one or more hydrogen atoms are substituted by a halogen atom,
monovalent heterocyclic groups and the like).
[0027] Among structures of the above-described formula (B),
structures of the following formula (1) are preferable.
##STR00007##
(wherein, A.sub.1 represents a hydrogen atom, alkyl group, aryl
group, arylalkyl group, aryloxyalkyl group, monovalent heterocyclic
group or divalent group. R represents a hydrogen atom, alkyl group,
alkoxy group, alkylthio group, alkylsilyl group, alkylamino group,
aryl group, aryloxy group, arylalkyl group, arylalkoxy group,
arylalkenyl group, arylalkynyl group, arylamino group, monovalent
heterocyclic group or cyano group. Z*s represent each independently
a direct bond or R. J and K represent each independently an integer
from 0 to 3. J1 and K1 represent each independently 0 or 1. When a
plurality of Rs are present, they may be the same or
different.).
[0028] In the above-described formula (1), J and K represent each
independently an integer from 0 to 3. When the structure of the
above-described formula (1) is a structure of the above-described
formula (2), J and K in the formula (1) represent an integer from 0
to 3, and J1 and K1 are both 1, and Z represent a direct bond
(namely, connecting bond). In this case, J and K in the
above-mentioned formula (1) are preferably 0 from the standpoint of
easiness of synthesis, and preferably 1 to 3 from the standpoint of
solubility, light emitting efficiency and the like.
[0029] In the above-described formula (A), Ar represents an arylene
group, divalent heterocyclic group, divalent aromatic amine group
or divalent group having a metal complex structure.
[0030] The arylene group is an atomic group in which two hydrogen
atoms of an aromatic hydrocarbon are removed, and usually, the
number of carbon atoms is about 6 to 60. The number of carbon atoms
does not include the number of carbon atoms of substituents. The
aromatic hydrocarbon includes those having a condensed ring, an
independent benzene ring, or two or more condensed rings bonded
through groups, such as a direct bond or a vinylene group.
[0031] Examples of the arylene group include phenylene group (for
example, following formulas 1-3), naphthalenediyl group (following
formulas 4-13), anthracenylene group (following formulas 14-19),
biphenylene group (following formulas 20-25), triphenyl group
(following formulas 26-28), condensed ring compound group
(following formulas 29-38), stilbene-diyl (following formulas A-D),
distilbene-diyl (following formulas E, F), benzofluorene-diyl
(following formulas G, H, I, K), etc.
[0032] Among them, phenylene group, biphenylene group,
fluorene-diyl group (following formulas 36-38), stilbene-diyl group
(following formulas A-D), distilbene-diyl (following formulas E,
F), benzofluorene-diyl (following formulas G, H, I, K), are
preferable.
##STR00008## ##STR00009## ##STR00010## ##STR00011## ##STR00012##
##STR00013## ##STR00014## ##STR00015##
[0033] In the above-mentioned formulae 1 to 38 and A to K, R
represents a hydrogen atom, alkyl group, alkoxy group, alkylthio
group, alkylsilyl group, alkylamino group, aryl group, aryloxy
group, arylalkyl group, arylalkoxy group, arylalkenyl group,
arylalkynyl group, arylamino group, monovalent heterocyclic group
or cyano group. When a plurality of Rs are present, they may be the
same or different.
[0034] Here, the alkyl group may be any of linear, branched or
cyclic, and has a carbon number of usually about 1 to 20, and as
specific examples thereof, a methyl group, ethyl group, propyl
group, i-propyl group, butyl group, i-butyl group, t-butyl group,
pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl
group, 2-ethylhexyl group, nonyl group, decyl group,
3,7-dimethyloctyl group, lauryl group and the like are mentioned,
and preferable are a pentyl group, hexyl group, octyl group,
2-ethylhexyl group, decyl group and 3,7-dimethyloctyl group.
[0035] The alkoxy group may be any of linear, branched or cyclic,
and has a carbon number of usually about 1 to 20, and as specific
examples thereof, a methoxy group, ethoxy group, propyloxy group,
i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group,
pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy
group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group,
decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group and the
like are mentioned, and preferable are a pentyloxy group, hexyloxy
group, octyloxy group, 2-ethylhexyloxy group, decyloxy group and
3,7-dimethyloctyloxy group.
[0036] The alkylthio group may be any of linear, branched or
cyclic, and has a carbon number of usually about 1 to 20, and as
specific examples thereof, a methylthio group, ethylthio group,
propylthio group, i-propylthio group, butylthio group, i-butylthio
group, t-butylthio group, pentylthio group, hexylthio group,
cyclohexylthio group, heptylthio group, octylthio group,
2-ethylhexylthio group, nonylthio group, decylthio group,
3,7-dimethyloctylthio group, laurylthio group and the like are
mentioned, and preferable are a pentylthio group, hexylthio group,
octylthio group, 2-ethylhexylthio group, decylthio group and
3,7-dimethyloctylthio group.
[0037] The alkylsilyl group may be any of linear, branched or
cyclic, and has a carbon number of usually about 1 to 60, and as
specific examples thereof, a methylsilyl group, ethylsilyl group,
propylsilyl group, i-propylsilyl group, butylsilyl group,
i-butylsilyl group, t-butylsilyl group, pentylsilyl group,
hexylsilyl group, cyclohexylsilyl group, heptylsilyl group,
octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group,
decylsilyl group, 3,7-dimethyloctylsilyl group, laurylsilyl group,
trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl
group, i-propyldimethylsilyl group, butyldimethylsilyl group,
t-butyldimethylsilyl group, pentyldimethylsilyl group,
hexyldimethylsilyl group, heptyldimethylsilyl group,
octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group,
nonyldimethylsilyl group, decyldimethylsilyl group,
3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group
and the like are mentioned, and preferable are a pentylsilyl group,
hexylsilyl group, octylsilyl group, 2-ethylhexylsilyl group,
decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl
group, hexyldimethylsilyl group, octyldimethylsilyl group,
2-ethylhexyl-dimethylsilyl group, decyldimethylsilyl group and
3,7-dimethyloctyl-dimethylsilyl group.
[0038] The alkylamino group may be any of linear, branched or
cyclic and may be a monoalkylamino group or dialkylamino group, and
has a carbon number of usually about 1 to 40, and specific examples
thereof, a methylamino group, dimethylamino group, ethylamino
group, diethylamino group, propylamino group, i-propylamino group,
butylamino group, i-butylamino group, t-butylamino group,
pentylamino group, hexylamino group, cyclohexylamino group,
heptylamino group, octylamino group, 2-ethylhexylamino group,
nonylamino group, decylamino group, 3,7-dimethyloctylamino group,
laurylamino group and the like, and preferable are a pentylamino
group, hexylamino group, octylamino group, 2-ethylhexylamino group,
decylamino group and 3,7-dimethyloctylamino group.
[0039] The aryl group has a carbon number of usually about 6 to 60,
and specific examples thereof, a phenyl group, C.sub.1 to C.sub.12
alkoxyphenyl groups (C.sub.1 to C.sub.12 means a carbon number of 1
to 12. Applicable also in the later descriptions), C.sub.1 to
C.sub.12 alkylphenyl groups, 1-naphthyl group, 2-naphthyl group and
the like are exemplified, and preferable are C.sub.1 to C.sub.12
alkoxyphenyl groups and C.sub.1 to C.sub.12 alkylphenyl groups.
[0040] The aryloxy group has a carbon number of usually about 6 to
60, and as specific examples thereof, a phenoxy group, C.sub.1 to
C.sub.12 alkoxyphenoxy groups, C.sub.1 to C.sub.12 alkylphenoxy
groups, 1-naphthyloxy group, 2-naphthyloxy group and the like are
exemplified, and preferable are C.sub.1 to C.sub.12 alkoxyphenoxy
groups and C.sub.1 to C.sub.12 alkylphenoxy groups.
[0041] The arylalkyl group has a carbon number of usually about 7
to 60, and as specific examples thereof, phenyl-C.sub.1 to C.sub.12
alkyl groups, C.sub.1 to C.sub.12 alkoxyphenyl-C.sub.1 to C.sub.12
alkyl groups, C.sub.1 to C.sub.12 alkylphenyl-C.sub.1 to C.sub.12
alkyl groups, 1-naphthyl-C.sub.1 to C.sub.12 alkyl groups,
2-naphthyl-C.sub.1 to C.sub.12 alkyl groups and the like are
exemplified, and preferable are C.sub.1 to C.sub.12
alkoxyphenyl-C.sub.1 to C.sub.12 alkyl groups and C.sub.1 to
C.sub.12 alkylphenyl-C.sub.1 to C.sub.12 alkyl groups.
[0042] The arylalkoxy group has a carbon number of usually about 7
to 60, and as specific examples thereof, phenyloxy-C.sub.1 to
C.sub.12 alkoxy groups, C.sub.1 to C.sub.12 alkoxyphenyl-C.sub.1 to
C.sub.12 alkoxy groups, C.sub.1 to C.sub.12 alkylphenyl-C.sub.1 to
C.sub.12 alkoxy groups, 1-naphthyl-C.sub.1 to C.sub.12 alkoxy
groups, 2-naphthyl-C.sub.1 to C.sub.12 alkoxy groups and the like
are exemplified, and preferable are C.sub.1 to C.sub.12
alkoxyphenyl-C.sub.1 to C.sub.12 alkoxy groups and C.sub.1 to
C.sub.12 alkylphenyl-C.sub.1 to C.sub.12 alkoxy groups.
[0043] The arylalkenyl group has a carbon number of usually about 8
to 60, and as specific examples thereof, phenyl-C.sub.2 to C.sub.12
alkenyl groups, C.sub.1 to C.sub.12 alkoxyphenyl-C.sub.2 to
C.sub.12 alkenyl groups, C.sub.1 to C.sub.12 alkylphenyl-C.sub.2 to
C.sub.12 alkenyl groups, 1-naphthyl-C.sub.2 to C.sub.12 alkenyl
groups, 2-naphthyl-C.sub.2 to C.sub.12 alkenyl groups and the like
are exemplified, and preferable are C.sub.1 to C.sub.12
alkoxyphenyl-C.sub.2 to C.sub.12 alkenyl groups and C.sub.1 to
C.sub.12 alkylphenyl-C.sub.2 to C.sub.12 alkenyl groups.
[0044] The arylalkynyl group has a carbon number of usually about 8
to 60, and as specific examples thereof, phenyl-C.sub.2 to C.sub.12
alkynyl groups, C.sub.1 to C.sub.12 alkoxyphenyl-C.sub.2 to
C.sub.12 alkynyl groups, C.sub.1 to C.sub.12 alkylphenyl-C.sub.2 to
C.sub.12 alkynyl groups, 1-naphthyl-C.sub.2 to C.sub.12 alkynyl
groups, 2-naphthyl-C.sub.2 to C.sub.12 alkynyl groups and the like
are exemplified, and preferable are C.sub.1 to C.sub.12
alkoxyphenyl-C.sub.2 to C.sub.12 alkynyl groups and C.sub.1 to
C.sub.12 alkylphenyl-C.sub.2 to C.sub.12 alkynyl groups.
[0045] The arylamino group has a carbon number of usually about 6
to 60, and a phenylamino group, diphenylamino group, C.sub.1 to
C.sub.12 alkoxyphenylamino groups, di(C.sub.1 to C.sub.12
alkoxyphenyl)amino groups, di(C.sub.1 to C.sub.12 alkylphenyl)amino
groups, 1-naphthylamino group, 2-naphthylamino group and the like
are exemplified, and preferable are C.sub.1 to C.sub.12
alkylphenylamino groups and di(C.sub.1 to C.sub.12
alkylphenyl)amino groups.
[0046] The monovalent heterocyclic group means an atom group
remaining after removal of one hydrogen atom from a heterocyclic
compound. The monovalent heterocyclic group has a carbon number of
usually about 4 to 60, and specifically, a thienyl group, C.sub.1
to C.sub.12 alkylthienyl groups, pyrrolyl group, furyl group,
pyridyl group, C.sub.1 to C.sub.12 alkylpyridyl groups and the like
are exemplified, and preferable are a thienyl group, C.sub.1 to
C.sub.12 alkylthienyl groups, pyridyl group and C.sub.1 to C.sub.12
alkylpyridyl groups.
[0047] When the above-mentioned substituent contains an alkyl
chain, this alkyl chain may be interrupted by a hetero atom or a
group containing a hetero atom. Here, exemplified as the hetero
atom are an oxygen atom, sulfur atom, nitrogen atom and the like.
As the hetero atom or group containing a hetero atom, for example,
the following groups are mentioned.
##STR00016##
[0048] Here, examples of R' include a hydrogen atom, alkyl groups
having 1 to 20 carbon atoms, aryl groups having 6 to 60 carbon
atoms and monovalent heterocyclic groups having 4 to 60 carbon
atoms.
[0049] The divalent heterocyclic group means an atomic group in
which two hydrogen atoms are removed from a heterocyclic compound,
and the number of carbon atoms is usually about 4 to 60. The number
of carbon atoms does not include the number of carbon atoms of
substituents.
[0050] The heterocyclic compound means an organic compound having a
cyclic structure in which at least one heteroatom such as oxygen,
sulfur, nitrogen, phosphorus, boron, etc. is contained in the
cyclic structure as the element other than carbon atoms.
[0051] Examples of the divalent heterocyclic groups include the
followings.
[0052] Groups containing nitrogen as a hetero atom; pyridine-diyl
group (following formulas 39-44), diazaphenylene group (following
formulas 45-48), quinolinediyl group (following formulas 49-63),
quinoxalinediyl group (following formulas 64-68), acridinediyl
group (following formulas 69-72), bipyridyldiyl group (following
formulas 73-75), phenanthrolinediyl group (following formulas
76-78), etc.
[0053] Groups having a fluorene structure containing silicon,
nitrogen, oxygen, sulfur, selenium, etc. as a hetero atom
(following formulas 79-93).
[0054] 5 membered heterocyclic groups containing silicon, nitrogen,
oxygen, sulfur, selenium, etc. as a hetero atom: (following
formulas 94-98).
[0055] Condensed 5 membered heterocyclic groups containing silicon,
nitrogen, oxygen, sulfur, selenium, etc. as a hetero atom:
(following formulas 99-108),
[0056] 5 membered heterocyclic groups containing sulfur, etc. as a
hetero atom, which are connected at the .alpha. position of the
hetero atom to form a dimer or an oligomer (following formulas
109-110); and
[0057] 5 membered ring heterocyclic groups containing silicon,
nitrogen, oxygen, sulfur, selenium, as a hetero atom is connected
with a phenyl group at the .alpha. position of the hetero atom
(following formulas 111-117).
##STR00017## ##STR00018## ##STR00019## ##STR00020## ##STR00021##
##STR00022## ##STR00023## ##STR00024## ##STR00025## ##STR00026##
##STR00027## ##STR00028##
In the above-described formulae 39 to 117, R represents the same
meaning as described above.
[0058] The divalent aromatic amine group means an atom group
remaining after removal of two hydrogen atoms from an aromatic
amine, and has a carbon number of usually about 4 to 60, and the
carbon number does not include the number of carbon atoms in a
substituent. As the divalent aromatic amine group, for example,
groups of the following general formula (5) are mentioned.
##STR00029##
[0059] In the formula, Ar.sub.5 and Ar.sub.7 represent each
independently an arylene group optionally having a substituent, a
group of the general formula (6) or a group of the general formula
(7). Ar.sub.5 represents an arylene group optionally having a
substituent, a group of the general formula (8) or a group of the
general formula (9). A ring may be formed between Ar.sub.5 and
Ar.sub.6, between Ar.sub.5 and Ar.sub.7, or between Ar.sub.6 and
Ar.sub.7.
##STR00030##
[0060] In the formula, Ar.sub.8 and Ar.sub.g represent each
independently an arylene group optionally having a substituent.
R.sub.7 and R.sub.8 represent each independently a hydrogen atom,
alkyl group, aryl group, monovalent heterocyclic group or cyano
group. l is 0 or 1.
##STR00031##
[0061] In the formula, Ar.sub.10 and Ar.sub.11 represent each
independently an arylene group optionally having a substituent.
Ar.sub.12 is an aryl group optionally having a substituent. A ring
may be formed between Ar.sub.10 and Ar.sub.12, between Ar.sub.10
and Ar.sub.11, or between Ar.sub.11 and Ar.sub.12.
##STR00032##
[0062] In the formula, Ar.sub.13 represents an arylene group
optionally having a substituent. Ar.sub.16 and Ar.sub.17 represent
each independently an aryl group optionally having a substituent. A
ring may be formed between Ar.sub.13 and Ar.sub.16, between
Ar.sub.13 and Ar.sub.17, or between Ar.sub.16 and Ar.sub.17.
##STR00033##
[0063] In the formula, Ar.sub.14 represents an arylene group
optionally having a substituent. Ar.sub.15 represents an aryl group
optionally having a substituent. R.sub.11 and R.sub.12 represent
each independently a hydrogen atom, alkyl group, aryl group,
monovalent heterocyclic group or cyano group. r is 0 or 1.
[0064] Ar.sub.5, Ar.sub.7 in the above-described formula (5),
Ar.sub.8, Ar.sub.g in the above-described formula (6), Ar.sub.10,
Ar.sub.11 in the above-described formula (7), Ar.sub.13 in the
above-described formula (8) and Ar.sub.14 in the above-described
formula (9) may have a substituent such as an alkyl group, alkoxy
group, alkylthio group, alkylsilyl group, alkylamino group, aryl
group, aryloxy group, arylalkyl group, arylalkoxy group,
arylalkenyl group, arylalkynyl group, arylamino group, monovalent
heterocyclic group, cyano group or the like.
[0065] Ar.sub.6 in the above-described formula (5), Ar.sub.12 in
the above-described formula (7), Ar.sub.16, Ar.sub.17 in the
above-described formula (8) and Ar.sub.15 in the above-described
formula (9) may have a substituent such as an alkyl group, alkoxy
group, alkylthio group, alkylsilyl group, alkylamino group, aryl
group, aryloxy group, arylalkyl group, arylalkoxy group,
arylalkenyl group, arylalkynyl group, arylamino group, monovalent
heterocyclic group, cyano group or the like.
[0066] As the divalent aromatic amine group, specifically, the
following groups are exemplified.
##STR00034##
[0067] In the above-described formulae 118 to 122, R represents the
same meaning as described above.
[0068] Here, for enhancing solubility of a polymer compound of the
present invention in solvents, it is preferable that the shape of a
repeating unit has little symmetry, and it is preferable that a
cyclic or branched alkyl chain is contained in one or more Rs. A
plurality of Rs may be coupled to form a ring.
[0069] Substituents containing an alkyl chain, among groups
represented by R, may be any of linear, branched or cyclic or a
combination thereof. In the case of non-linear, exemplified are an
isoamyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group,
cyclohexyl group, 4-C.sub.1 to C.sub.12 alkylcyclohexyl groups and
the like.
[0070] The divalent group having a metal complex structure means a
divalent group remaining after removal of two hydrogen atoms from
an organic ligand of a metal complex having an organic ligand.
[0071] The carbon number of the organic ligand is usually about 4
to 60, and examples thereof include 8-quinolinol and derivatives
thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine
and derivatives thereof, 2-phenyl-benzothiazole and derivatives
thereof, 2-phenyl-benzoxazole and derivatives thereof, porphyrin
and derivatives thereof, and the like.
[0072] Mentioned as the center metal of the complex are, for
example, aluminum, zinc, beryllium, iridium, platinum, gold,
europium, terbium and the like.
[0073] As the metal complex having an organic ligand, mentioned are
metal complexes, triplet light emitting complexes and the like
known as fluorescent materials and phosphorescent materials of
lower molecular weight.
[0074] As the divalent group having a metal complex structure, the
following groups 126 to 132 are specifically exemplified.
##STR00035## ##STR00036## ##STR00037##
[0075] In the above-described formulae 126 to 132, exemplified as R
are the same groups as described above.
[0076] Among polymer compounds of the present invention, those
containing a repeating unit of the above-mentioned formula (2) are
preferable from the standpoint of change of light emitting
wavelength.
[0077] From the standpoint of easiness of control of light emitting
wavelength, easiness of control of molecular weight and easiness of
synthesis, a polymer compound composed of a repeating unit of the
above-described formula (2) wherein m is 0 is preferable.
##STR00038##
[0078] Z represents --CR.sub.3.dbd.CR.sub.4-- or --C.ident.C--.
R.sub.3 and R.sub.4 represent each independently a hydrogen atom,
alkyl group, aryl group, monovalent heterocyclic group or cyano
group. m represents 0 or 1. It is preferable that m is 0 from the
standpoint of photooxidation stability. A.sub.1 and R represent the
same meanings as described above. j and k represent each
independently an integer of 0 to 3. From the standpoint of easiness
of synthesis, 0 is preferable and from the standpoint of
solubility, light emitting efficiency and the like, 1 to 3 are
preferable.
[0079] Specific examples of the repeating unit of the formula (2)
are shown below.
##STR00039## ##STR00040## ##STR00041##
[0080] Among polymer compounds of the present invention, preferable
are those containing further a repeating unit of the following
formula (30) from the standpoint of enhancement of light emitting
efficiency and change of light emitting wavelength.
--Ar.sub.1--(Z')p- (30)
[0081] Ar.sub.1 in the above-described formula (30) is an arylene
group, divalent heterocyclic group or divalent aromatic amine
group. The arylene group, divalent heterocyclic group and divalent
aromatic amine group represented by Ar.sub.1 are the same groups as
described and exemplified for the above-mentioned Ar.
[0082] In the above-described formula (30), Z' represents
--CR.sub.5.dbd.CR.sub.6-- or --C.ident.C--. R.sub.5 and R.sub.6
represent each independently a hydrogen atom, alkyl group, aryl
group, monovalent heterocyclic group or cyano group. p represents 0
or 1. --CR.sub.5.dbd.CR.sub.6-- is preferable from the standpoint
of stability. --CR.sub.5.dbd.CR.sub.6-- is preferable from the
standpoint of elongation of light emitting wavelength. From the
standpoint of photooxidation stability, it is more preferable that
p is 0.
[0083] The total amount of repeating units of the above-described
formula (2) is 0.1 mol % or more and 100 mol % or less, preferably
1 mol % or more and 100 mol % or less based on all repeating
units.
[0084] Among polymer compounds containing repeating units of the
formulae (2) and (30), those in which the total amount of repeating
units of the formulae (2) and (30) is 50 mol % or more based on all
repeating units are more preferable from the standpoint of light
emitting efficiency. Additionally, those in which the amount of a
repeating unit of the formula (2) is 0.1 mol % or more and 90 mol %
or less based on the total amount of repeating units of the
formulae (2) and (30) are more preferable from the standpoint of
light emitting efficiency.
[0085] Substantially, preferable as those composed of repeating
units of the formulae (2) and (30) are specifically copolymers
composed of one more groups selected from the following examples as
the repeating unit of the formula (2):
##STR00042##
and one or more groups selected from the following examples as the
repeating unit of the formula (30):
##STR00043## ##STR00044##
(wherein, R represents the same meaning as described above.).
[0086] Among polymer compounds of the present invention, those
containing a repeating unit of the following formula (3) are
preferable from the standpoint of light emitting efficiency.
##STR00045##
(wherein, A.sub.2 represents a group of the following formula
(4):
*--(Ar.sub.1)j.sub.1-(X)k.sub.1-(Ar.sub.2)p.sub.1-(Y)q.sub.1-
(4)
(wherein, Ar.sub.1 and Ar.sub.2 represent each independently an
arylene group, divalent heterocyclic group or divalent aromatic
amine group, X represents --R.sub.7--, --O--R.sub.7--,
--R.sub.7--O--, --R.sub.7--C(O)O--, --R.sub.7--OC(O)--,
--R.sub.7--N(R.sub.20)--, --O--, --S--, --C(O)O-- or --C(O)--, Y
represents --C(R.sub.20).dbd.C(R.sub.20)-- or --C.ident.C--,
j.sub.1, k.sub.1, p.sub.1 and q.sub.1 are each independently 0 or
1, R.sub.7 represents an alkylene group, R.sub.20 represents a
hydrogen atom, alkyl group, aryl group, monovalent heterocyclic
group or cyano group, and represents a site to be connected to N.),
n.sub.1 and n.sub.2 represent each independently 0 or 1, and R is
as described above, and a plurality of Rs may be the same or
different.).
[0087] A.sub.2 in the above-described formula (3) is a group of the
above-described formula (4).
[0088] Ar.sub.1 and Ar.sub.2 in the above-described formula (4)
represent each independently an arylene group, divalent
heterocyclic group or divalent aromatic amine group. Here, Ar.sub.1
and Ar.sub.2 may have a substituent such as an alkyl group, alkoxy
group, alkylthio group, alkylsilyl group, alkylamino group, aryl
group, aryloxy group, arylalkyl group, arylalkoxy group,
arylalkenyl group, arylalkynyl group, arylamino group, monovalent
heterocyclic group or the like. When Ar.sub.1 and Ar.sub.2 have a
plurality of substituents, these substituents may be the same or
different.
[0089] In the above-described formula (4), the arylene group means
an atom group remaining after removal of two hydrogen atoms from an
aromatic hydrocarbon, and has a carbon number of usually about 6 to
60. The carbon number does not include the number of carbon atoms
in a substituent. Also included as the aromatic hydrocarbon here
are those having a condensed ring, and those in which two or more
independent benzene rings or condensed rings are connected directly
or via a group such as a vinylene group and the like. As specific
examples of the arylene group, the formulae 1 to 38 and A to K as
illustrated above are mentioned. The divalent heterocyclic group is
the same as described for the above-mentioned formula (1), and as
specific examples thereof, the formulae 39 to 117 as illustrated
above are mentioned. The divalent aromatic amine group is the same
as described for the above-mentioned formula (1), and as specific
examples thereof, the formulae 118 to 122 as illustrated above are
mentioned.
[0090] In the above-described formula (4), X represents
--R.sub.7--, --O--R.sub.7--, --R.sub.7--O--, --R.sub.7--C(O)O--,
--R.sub.7--OC(O)--, --R.sub.7--N(R.sub.20)--, --O--, --S--,
--C(O)O-- or --C(O)--. R.sub.7 represents an alkylene group. From
the standpoint of solubility and easiness of synthesis, --R.sub.7--
and --R.sub.7--O-- are preferable.
[0091] In the above-described formula (4), Y represents
--C(R.sub.20).dbd.C(R.sub.20)-- or --C.ident.C--. R.sub.20
represents a hydrogen atom, alkyl group, aryl group, monovalent
heterocyclic group or cyano group. --C(R.sub.20).dbd.C(R.sub.20)--
is preferable from the standpoint of stability.
[0092] In the above-described formula (4), j.sub.1, k.sub.1,
p.sub.1 and q.sub.1 represent each independently 0 or 1. From the
standpoint of light emitting efficiency, solubility and easiness of
synthesis, it is preferable that q.sub.1 is 0, k.sub.1 is 1 and X
is --R.sub.7-- or --R.sub.7--O--. It is more preferable that
q.sub.1 is 0, p.sub.1 is 1, Ar.sub.2 is phenylene and X is
--R.sub.7-- or --R.sub.7--O--. Further, from the standpoint of
stability, q.sub.1 is preferably 0.
[0093] In the above-described formula (3), n.sub.1 and n.sub.2
represent each independently 0 or 1. From the standpoint of light
emitting efficiency, solubility and easiness of synthesis, at least
one of n.sub.1 and n.sub.2 is 1. It is more preferable that n.sub.1
and n.sub.2 both represent 1.
[0094] The total amount of repeating units of the formula (3) is
preferably 0.1 mol % or more and 100 mol % or less based on all
repeating units.
[0095] From the standpoint of change of light emitting wavelength,
preferable are polymer compounds composed of a repeating unit of
the above-described formula (3) wherein n.sub.1 and n.sub.2 both
represent 0.
[0096] Among polymer compounds of the present invention, also
preferable are those containing further a repeating unit of the
following formula (31) from the standpoint of enhancement of light
emitting efficiency and change of light emitting wavelength.
--Ar.sub.4--(Z).sub.t-- (31)
(wherein, Ar.sub.4 represents an arylene group, divalent
heterocyclic group or divalent aromatic amine group. Z represents
--CR.sub.8.dbd.CR.sub.9-- or --C.ident.C--. R.sub.8 and R.sub.9
represent each independently a hydrogen atom, alkyl group, aryl
group, monovalent heterocyclic group or cyano group. t represents 0
or 1).
[0097] As the repeating unit of the formula (31), specifically
mentioned are those having structures described in the
above-mentioned formulae 1 to 117, the above-mentioned formulae A
to I and K, the above-mentioned formulae 118 to 122, and formulae
133 to 140 described later. Among others, preferable are phenylene
groups (e.g., formulae 1 to 3 as illustrated above),
naphthalenediyl groups (formulae 4 to 13 as illustrated above),
anthracenylene groups (formulae 14 to 19 as illustrated above),
biphenylene groups (formulae 20 to 25 as illustrated above),
triphenylene groups (formulae 26 to 28 as illustrated above),
confused ring compound groups (formulae 29 to 38 as illustrated
above), dibenzofuran-diyl groups (formulae 85 to 87 as illustrated
above), dibenzothiophene-diyl groups (formulae 88 to 90 as
illustrated above), stilbene-diyl groups (A to D as illustrated
above), distilbene-diyl groups (E, F as illustrated above),
benzofluorene-diyl groups (G, H, I, K as illustrated above),
divalent aromatic amine groups (formulae 118 to 119 and 122 as
illustrated above), arylenevinylene groups (formulae 133 to 140 as
illustrated below) and the like, and particularly, phenylene
groups, biphenylene groups, fluorene-diyl groups (formulae 36 to 38
as illustrated above), dibenzofuran-diyl groups (formulae 85 to 87
as illustrated above), dibenzothiophene-diyl groups (formulae 88 to
90 as illustrated above), stilbene-diyl groups (A to D as
illustrated above), distilbene-diyl groups (E, F as illustrated
above), benzofluorene-diyl groups (G, H, I, K as illustrated above)
and divalent aromatic amine groups are preferable.
##STR00046## ##STR00047##
[0098] Here, R represents the same meaning as described above.
[0099] For enhancing solubility of a polymer compound of the
present invention in solvents, it is preferable that the shape of a
repeating unit has little symmetry, and it is preferable that a
cyclic or branched alkyl chain is contained in one or more Rs. A
plurality of Rs may be coupled to form a ring. Substituents
containing an alkyl chain, among groups represented by R, may be
any of linear, branched or cyclic or a combination thereof. In the
case of non-linear, exemplified are an isoamyl group, 2-ethylhexyl
group, 3,7-dimethyloctyl group, cyclohexyl group, 4-C.sub.1 to
C.sub.12 alkylcyclohexyl groups and the like.
[0100] Substantially, exemplified as those composed of repeating
units of the formulae (3) and (31) are specifically copolymers
composed of one more groups selected from the following examples as
the repeating unit of the formula (3):
##STR00048## ##STR00049##
(wherein, R and R.sub.7 represent the same meanings as described
above.) and one or more groups selected from the following examples
as the repeating unit of the formula (31):
##STR00050## ##STR00051##
(wherein, R represents the same meaning as described above.).
[0101] Among polymer compounds containing repeating units of the
formulae (3) and (31), those in which the total amount of repeating
units of the formulae (3) and (31) is 50 mol % or more based on all
repeating units are more preferable from the standpoint of light
emitting efficiency. Additionally, those in which the amount of a
repeating unit of the formula (3) is 0.1 mol % or more and 90 mol %
or less based on the total amount of repeating units of the
formulae (3) and (31) are more preferable from the standpoint of
light emitting efficiency.
[0102] The polymer compound of the present invention has a
polystyrene reduced number average molecular weight of typically
10.sup.3 to 10.sup.8, preferably 2.times.10.sup.3 to 10.sup.7.
[0103] When a polymerization active group remains intact at an end
group of a polymer compound of the present invention, there is a
possibility of lowering of light emitting property and life when
made into a device, thus, the end group may be protected by a
stable group. Those having a conjugated bond consecutive to a
conjugation structure of the main chain are preferable, and for
example, structures connected to an aryl group or heterocyclic
group via a vinylene group may be permissible. Specifically,
substituents described in chemical formula 10 of Japanese Patent
Application Laid-Open (JP-A) No. 9-45478 and the like are
exemplified.
[0104] The polymer compound of the present invention may contain
repeating units other than the repeating units of the
above-described formulae (3) and (31) in a range not deteriorating
fluorescent property and charge transporting property, however,
those composed substantially of a repeating unit of the formula (1)
and those composed substantially of repeating units of the formulae
(3) and (31) are preferable.
[0105] Repeating units may be connected via a vinylene or
nonconjugated portion, or repeating units may contain a vinylene or
nonconjugated portion. As the connected structure containing a
nonconjugated portion, exemplified are those shown later,
combinations of those shown later with a vinylene group, and
combinations of two or more of those shown below, and the like.
Here, R represents a group selected from the same substituents as
described above, and Ar' represents a hydrocarbon group having 6 to
60 carbon atoms.
##STR00052##
[0106] The polymer compound of the present invention may be a
random, block or graft copolymer, or a polymer having an
intermediate structure between them, for example, a random
copolymer taking on a blocking property. From the standpoint of
obtaining a polymer compound having high fluorescent quantum yield,
a random copolymer taking on a blocking property, and a block or
graft copolymer are more preferable than complete random
copolymers. Those having branching in the main chain and having
three or more ends, and dendrimers are also included.
[0107] When the polymer compound of the present invention is used
as a light emitting material of a polymer LED, luminescence or
phosphorescence from a thin film is utilized, thus, those showing
fluorescence or phosphorescence at solid state are preferable as
the polymer compound of the present invention.
[0108] As the good solvent for the polymer compound of the present
invention, chloroform, methylene chloride, dichloroethane,
tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin,
n-butylbenzene and the like are exemplified. Depending on the
structure and molecular weight of the polymer compound, the polymer
compound can be dissolved in these solvents usually in an amount of
0.1 wt % or more.
[0109] Next, the method for producing a polymer compound of the
present invention will be described.
[0110] A polymer compound of the present invention containing a
repeating unit of the above-described formula (2) can be produced,
for example, by condensation-polymerizing a compound of the
following formula as one of raw materials.
##STR00053##
(wherein, R, j, k and A.sub.1 are as in the formula (2). D.sub.1
and D.sub.2 represent each independently a halogen atom, alkyl
sulfonate group, aryl sulfonate group, aryl alkyl sulfonate group,
borate group, sulfoniummethyl group, phosphoniummethyl group,
phosphonatemethyl group, methyl monohalide group, boric group,
formyl group, cyanomethyl group or vinyl group.).
[0111] Here, examples of the alkylsulfonate group include a methane
sulfonate group, ethane sulfonate group, trifluoromethane sulfonate
group and the like, and examples of the aryl sulfonate group
include a benzene sulfonate group, p-toluene sulfonate group and
the like, and examples of the aryl alkyl sulfonate group include a
benzyl sulfonate group and the like.
[0112] As the borate group, groups of the following formulae are
exemplified.
##STR00054##
[0113] As the sulfoniummethyl group, groups of the following
formulae are exemplified.
--CH.sub.2S.sup.+Me.sub.2Xh.sup.-,
--CH.sub.2S.sup.+Ph.sub.2Xh.sup.-(Xh represents a halogen atom)
[0114] As the phosphoniummethyl group, groups of the following
formula are exemplified.
--CH.sub.2P.sup.+Ph.sub.2Xh.sup.-(Xh represents a halogen atom)
[0115] As the phosphonatemethyl group, groups of the following
formula are exemplified.
--CH.sub.2PO(OR''').sub.2
(R''' represents an alkyl group, aryl group or arylalkyl
group.)
[0116] Examples of the methyl monohalide group include a methyl
fluoride group, methyl chloride group, methyl bromide group and
methyl iodide group.
[0117] Regarding the condensation polymerization method, when, for
example, the main chain has a vinylene group, other monomers are
used according to demands, and for example, methods such as [1]
polymerization by the Wittig reaction of a compound having an
aldehyde group and a compound having a phosphonium salt group, [2]
polymerization by the Wittig reaction of a compound having an
aldehyde group and a phosphonium salt group, [3] polymerization by
the Heck reaction of a compound having a vinyl group and a compound
having a halogen atom, [4] polymerization by the Heck reaction of a
compound having a vinyl group and a halogen atom, [5]
polymerization by the Horner-Wadsworth-Emmons method of a compound
having an aldehyde group and a compound having an alkyl sulfonate
group, [6] polymerization by the Horner-Wadsworth-Emmons method of
a compound having an aldehyde group and an alkyl sulfonate group,
[7] polycondensation by the dehydrohalogenation method of a
compound having two or more methyl halide groups, [8]
polycondensation by the sulfonium salt decomposition method of a
compound having two or more sulfonium salt groups, [9]
polymerization by the Knoevenagel reaction of a compound having an
aldehyde group and a compound having an acetonitrile group, [10]
polymerization by the Knoevenagel reaction of a compound having an
aldehyde group and an acetonitrile group, and the like, methods
such as [11] polymerization by the McMurry reaction of a compound
having two or more aldehyde groups, and the like, are
exemplified.
[0118] As the method for producing a polymer compound of the
present invention, for example, [12] a method of polymerization by
the Suzuki coupling reaction, [13] a method of polymerization by
the Grignard reaction, [14] a method of polymerization with a Ni(0)
catalyst, [15] a method of polymerization with an oxidizer such as
FeCl.sub.3 and the like, a method of electrochemical oxidation
polymerization, [16] a method by decomposition of an intermediate
polymer having a suitable leaving group, and the like, are
exemplified.
[0119] As the reaction using a Ni(0) catalyst, exemplified is a
method of polymerization in the presence of a zerovalent nickel
complex {Ni(COD).sub.2}.
[0120] As the zerovalent nickel complex,
bis(1,5-cyclooctadiene)nickel(0),
(ethylene)bis(triphenylphosphine)nickel(0),
tetrakis(triphenylphosphine)nickel and the like are exemplified,
and of them, bis(1,5-cyclooctadiene)nickel(0) is preferable from
the standpoint of general versatility and cheap price.
[0121] Addition of a neutral ligand is preferable from the
standpoint of improvement in yield.
[0122] Here, the neutral ligand is a ligand having no anion and
cation, and exemplified are nitrogen-containing ligands such as
2,2'-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline,
N,N'-tetramethylethylenediamine and the like; tertiary phosphine
ligands such as triphenylphosphine, tritolylphosphine,
tributylphosphine, triphenoxyphosphine and the like, and
nitrogen-containing ligands are preferable from the standpoint of
general versatility and cheap price, and 2,2'-bipyridyl is
particularly preferable from the standpoint of high reactivity and
high yield. Particularly, a system obtained by adding
2,2'-bipyridyl as a neutral ligand to a system containing
bis(1,5-cyclooctadiene)nickel(0) is preferable from the standpoint
of improvement in yield of a polymer.
[0123] The polymerization solvent is not particularly restricted
providing it does not disturb polymerization, and examples thereof
include amide solvents, aromatic hydrocarbon solvents, ether
solvents, ester solvents and the like.
[0124] Examples of the amide solvent include N,N-dimethylformamide,
N,N-dimethylacetamide and the like.
[0125] The aromatic hydrocarbon solvent is a solvent composed of an
aromatic hydrocarbon compound, and examples thereof include
benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene,
butylbenzene, naphthalene, tetralin and the like, and preferable
are toluene, xylene, tetralin, tetramethylbenzene and the like.
[0126] The ether solvent is a solvent composed of a compound in
which hydrocarbon groups are connected via an oxygen atom, and
examples thereof include diisopropyl ether, tetrahydrofuran,
1,4-dioxane, diphenyl ether, ethylene glycol dimethyl ether,
tert-butyl methyl ether and the like, and tetrahydrofuran,
1,4-dioxane and the like as a good solvent for a polymer compound
are preferable.
[0127] These solvents may be mixed and used from the standpoint of
improvement of polymerizability and solubility.
[0128] The polymerization reaction is carried out usually under an
atmosphere of an inert gas such as argon, nitrogen and the
like.
[0129] The polymerization time is usually about 0.5 to 100 hours,
and from the standpoint of production cost, times of 30 hours or
less are preferable.
[0130] The polymerization temperature is usually about 0 to
200.degree. C., and from the standpoint of high yield and low
heating cost, temperatures of 0 to 100.degree. C. are
preferable.
[0131] As the reaction in the presence of a Pd catalyst, for
example, the Suzuki coupling reaction is mentioned.
[0132] As the palladium catalyst used in the Suzuki coupling
reaction, exemplified are palladium acetate,
palladium[tetrakis(triphenylphosphine)] complex,
bis(tricyclohexylphosphine)palladium complex and the like.
[0133] As the phosphorus ligand, exemplified are
triphenylphosphine, tri(o-tolyl)phosphine,
1,3-bis(diphenylphosphino)propane and the like.
[0134] For example, palladium[tetrakis(triphenylphosphine)] is
used, and an inorganic salt group such as potassium carbonate,
sodium carbonate, barium hydroxide and the like, an organic salt
group such as triethylamine and the like, or an inorganic salt such
as cesium fluoride and the like is added in an amount of equivalent
or more, preferably 1 to 10 equivalents based on the monomer and
they are reacted. It may also be permissible that an inorganic salt
is used in the form of aqueous solution and the reaction is
performed in a two-phase system. Examples of the solvent include
N,N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran
and the like. Depending on the solvent, temperatures of about 50 to
160.degree. C. are suitably used. The mixture may be heated up to
near the boiling point of the solvent and refluxed. The reaction
time is about 1 hour to 200 hours.
[0135] Of them, preferable are the methods of polymerization by the
Wittig reaction, polymerization by the Heck reaction,
polymerization by the Horner-Wadsworth-Emmons method,
polymerization by the Knoevenagel reaction, polymerization by the
Suzuki coupling reaction, polymerization by the Grignard reaction
and polymerization with a Ni(0) catalyst because of easiness of
obtaining raw materials and simplicity of the polymerization
reaction operation.
[0136] After completion of production of a polymer compound of the
present invention, if necessary, the compound may be subjected to
conventional separation operations such as acid washing, alkali
washing, neutralization, water washing, organic solvent washing,
re-precipitation, centrifugal separation, extraction, column
chromatography and the like, purification operations, drying or
other operations.
[0137] When a polymer compound of the present invention is used as
a light emitting material of a polymer LED, its purity exerts an
influence on light emitting property, thus, it is preferable, in
the production method of the present invention, to perform the
above-mentioned separation operations and purification operations
sufficiently to remove unreacted monomers, by-products, catalyst
residues and the like sufficiently.
[0138] In drying, conditions for sufficient removal of the
remaining solvent are advantageous. For preventing degradation of a
polymer compound, it is preferable to provide shading and perform
drying in an inert atmosphere. It is preferable to perform drying
at temperatures not causing thermal degradation of a polymer
compound.
[0139] The polymer compound of the present invention can be used as
a light emitting material. Further, the polymer compound of the
present invention can be used also as a charge transporting
material, organic semiconductor material, optical material, or
electrically conductive material by doping.
[0140] By allowing at least one of the polymer compound of the
present invention and at least one material selected from the group
consisting of hole transporting materials, electron transporting
materials and light emitting materials to be contained, a
composition can be prepared. In the following descriptions,
"polymer compound" is a concept including a composition.
[0141] The polymer compound of the present invention is useful also
for production of thin films such as electrically conductive thin
films, organic semiconductor thin films and the like. These film
films have a thickness of usually 1 nm to 1 .mu.m, preferably 2 nm
to 500 nm. By using this organic semiconductor thin film, an
organic transistor having the organic semiconductor thin film can
be produce.
[0142] Next, the polymer LED of the present invention will be
described.
[0143] The polymer LED of the present invention is characterized in
that a light emitting layer is present between electrodes composed
of an anode and a cathode wherein the light emitting layer contains
a light emitting material of the present invention.
[0144] As the polymer LED of the present invention, mentioned are
polymer LED having an electron transporting layer provided between
a cathode and a light emitting layer, polymer LED having a hole
transporting layer provided between an anode and a light emitting
layer, polymer LED having an electron transporting layer provided
between a cathode and a light emitting layer and having a hole
transporting layer provided between an anode and a light emitting
layer.
[0145] Moreover, the polymer LED of the present invention include a
polymer-LED in which a layer containing a conductive polymer is
disposed between at least one of the above electrodes and a light
emitting layer adjacently to the electrode; and a polymer LED in
which a buffer layer having a mean film thickness of 2 nm or less
is disposed between at least one of the above electrodes and a
light emitting layer adjacently to the electrode.
[0146] Specifically, the following structures a)-d) are
exemplified.
a) anode/light emitting layer/cathode b) anode/hole transporting
layer/light emitting layer/cathode c) anode/light emitting
layer/electron transporting layer/cathode d) anode/hole
transporting layer/light emitting layer/electron transporting
layer/cathode (wherein, "/" indicates adjacent lamination of
layers. Hereinafter, the same).
[0147] Herein, the light emitting layer is a layer having function
to emit a light, the hole transporting layer is a layer having
function to transport a hole, and the electron transporting layer
is a layer having function to transport an electron. Herein, the
electron transporting layer and the hole transporting layer are
generically called a charge transporting layer. The light emitting
layer, hole transporting layer and electron transporting layer also
may be used each independently in two or more layers.
[0148] Charge transporting layers disposed adjacent to an
electrode, that having function to improve charge injecting
efficiency from the electrode and having effect to decrease driving
voltage of an device are particularly called sometimes a charge
injecting layer (hole injecting layer, electron injecting layer) in
general.
[0149] For enhancing adherence with an electrode and improving
charge injection from an electrode, the above-described charge
injecting layer or insulation layer having a thickness of 2 nm or
less may also be provided adjacent to an electrode, and further,
for enhancing adherence of the interface, preventing mixing and the
like, a thin buffer layer may also be inserted into the interface
of a charge transporting layer and light emitting layer.
[0150] The order and number of layers laminated and the thickness
of each layer can be appropriately applied while considering light
emitting efficiency and life of the device.
[0151] In the present invention, as the polymer LED having a charge
injecting layer (electron injecting layer, hole injecting layer)
provided, there are listed a polymer LED having a charge injecting
layer provided adjacent to a cathode and a polymer LED having a
charge injecting layer provided adjacent to an anode.
[0152] For example, the following structures e) to p) are
specifically exemplified.
e) anode/charge injecting layer/light emitting layer/cathode f)
anode/light emitting layer/charge injecting layer/cathode g)
anode/charge injecting layer/light emitting layer/charge injecting
layer/cathode h) anode/charge injecting layer/hole transporting
layer/light emitting layer/cathode i) anode/hole transporting
layer/light emitting layer/charge injecting layer/cathode j)
anode/charge injecting layer/hole transporting layer/light emitting
layer/charge injecting layer/cathode k) anode/charge injecting
layer/light emitting layer/electron transporting layer/cathode l)
anode/light emitting layer/electron transporting layer/charge
injecting layer/cathode m) anode/charge injecting layer/light
emitting layer/electron transporting layer/charge injecting
layer/cathode n) anode/charge injecting layer/hole transporting
layer/light emitting layer/electron transporting layer/cathode o)
anode/hole transporting layer/light emitting layer/electron
transporting layer/charge injecting layer/cathode p) anode/charge
injecting layer/hole transporting layer/light emitting
layer/electron transporting layer/charge injecting
layer/cathode
[0153] As the specific examples of the charge injecting layer,
there are exemplified layers containing an conducting polymer,
layers which are disposed between an anode and a hole transporting
layer and contain a material having an ionization potential between
the ionization potential of an anode material and the ionization
potential of a hole transporting material contained in the hole
transporting layer, layers which are disposed between a cathode and
an electron transporting layer and contain a material having an
electron affinity between the electron affinity of a cathode
material and the electron affinity of an electron transporting
material contained in the electron transporting layer, and the
like.
[0154] When the above-described charge injecting layer is a layer
containing an conducting polymer, the electric conductivity of the
conducting polymer is preferably 10.sup.-5 S/cm or more and
10.sup.3 S/cm or less, and for decreasing the leak current between
light emitting pixels, more preferably 10.sup.-5 S/cm or more and
10.sup.2 S/cm or less, further preferably 10.sup.-5 S/cm or more
and 10.sup.1 S/cm or less.
[0155] Usually, to provide an electric conductivity of the
conducting polymer of 10.sup.-5 S/cm or more and 10.sup.3 S/cm or
less, a suitable amount of ions are doped into the conducting
polymer.
[0156] Regarding the kind of an ion doped, an anion is used in a
hole injecting layer and a cation is used in an electron injecting
layer. As examples of the anion, a polystyrene sulfonate ion,
alkylbenzene sulfonate ion, camphor sulfonate ion and the like are
exemplified, and as examples of the cation, a lithium ion, sodium
ion, potassium ion, tetrabutyl ammonium ion and the like are
exemplified.
[0157] The thickness of the charge injecting layer is for example,
from 1 nm to 100 nm, preferably from 2 nm to 50 nm.
[0158] Materials used in the charge injecting layer may properly be
selected in view of relation with the materials of electrode and
adjacent layers, and there are exemplified conducting polymers such
as polyaniline and derivatives thereof, polythiophene and
derivatives thereof, polypyrrole and derivatives thereof,
poly(phenylene vinylene) and derivatives thereof, poly(thienylene
vinylene) and derivatives thereof, polyquinoline and derivatives
thereof, polyquinoxaline and derivatives thereof, polymers
containing aromatic amine structures in the main chain or the side
chain, and the like, and metal phthalocyanine (copper
phthalocyanine and the like), carbon and the like.
[0159] The insulation layer having a thickness of 2 nm or less has
function to make charge injection easy. As the material of the
above-described insulation layer, metal fluoride, metal oxide,
organic insulation materials and the like are listed. As the
polymer LED having an insulation layer having a thickness of 2 nm
or less, there are listed polymer LEDs having an insulation layer
having a thickness of 2 nm or less provided adjacent to a cathode,
and polymer LEDs having an insulation layer having a thickness of 2
nm or less provided adjacent to an anode.
[0160] Specifically, there are listed the following structures q)
to ab) for example.
q) anode/insulation layer having a thickness of 2 nm or less/light
emitting layer/cathode r) anode/light emitting layer/insulation
layer having a thickness of 2 nm or less/cathode s)
anode/insulation layer having a thickness of 2 nm or less/light
emitting layer/insulation layer having a thickness of 2 nm or
less/cathode t) anode/insulation layer having a thickness of 2 nm
or less/hole transporting layer/light emitting layer/cathode u)
anode/hole transporting layer/light emitting layer/insulation layer
having a thickness of 2 nm or less/cathode v) anode/insulation
layer having a thickness of 2 nm or less/hole transporting
layer/light emitting layer/insulation layer having a thickness of 2
nm or less/cathode w) anode/insulation layer having a thickness of
2 nm or less/light emitting layer/electron transporting
layer/cathode x) anode/light emitting layer/electron transporting
layer/insulation layer having a thickness of 2 nm or less/cathode
y) anode/insulation layer having a thickness of 2 nm or less/light
emitting layer/electron transporting layer/insulation layer having
a thickness of 2 nm or less/cathode z) anode/insulation layer
having a thickness of 2 nm or less/hole transporting layer/light
emitting layer/electron transporting layer/cathode aa) anode/hole
transporting layer/light emitting layer/electron transporting
layer/insulation layer having a thickness of 2 nm or less/cathode
ab) anode/insulation layer having a thickness of 2 nm or less/hole
transporting layer/light emitting layer/electron transporting
layer/insulation layer having a thickness of 2 nm or
less/cathode
[0161] The thickness of a light emitting layer in a polymer LED of
the present invention has an optimum value varying depending on a
material to be used and may be advantageously selected to give
suitable driving voltage and light emitting efficiency, and is, for
example, from 1 nm to 1 .mu.m, preferably from 2 nm to 500 nm,
further preferably from 5 nm to 200 nm.
[0162] In the polymer LED of the present invention, a light
emitting material other than the above-mentioned polymer compound
may be mixed and used in a light emitting layer. In the polymer LED
of the present invention, a light emitting layer containing a light
emitting material other than the above-mentioned polymer compound
may be laminated to a light emitting layer containing the
above-mentioned polymer compound.
[0163] As the light emitting material, known materials can be used.
In the case of a compound of lower molecular weight, there can be
used, for example, naphthalene derivatives, anthracene or
derivatives thereof, perylene or derivatives thereof; coloring
matters such as polymethine, xanthene, coumarin, cyanine and the
like; metal complexes of 8-hydroxyquinoline or derivatives thereof;
aromatic amines, tetraphenylcyclopentadiene or derivatives thereof,
tetraphenylbutadiene or derivatives thereof, metal complexes of
2-phenylpyridine or derivatives thereof, metal complexes of
acetylacetone or derivatives thereof, and the like.
[0164] Specifically, known compounds such as those described in,
for example, JP-A Nos. 57-51781 and 59-194393, and the like, can be
used.
[0165] When a film is formed from a solution by use of a polymer
compound of the present invention in producing a polymer LED, it
may be permissible that this solution is only dried after
application to remove a solvent, and also in the case of mixing of
a charge transporting material or light emitting material, the same
means can be applied, being very advantageous for production. As
the film formation method from a solution, application methods such
as a spin coat method, casting method, micro gravure coat method,
gravure coat method, bar coat method, roll coat method, wire bar
coat method, dip coat method, spray coat method, screen printing
method, flexographic printing method, offset printing method,
inkjet printing method and the like can be used.
[0166] In an ink composition (for example, used in the form of
solution in a printing method and the like), at least one of the
polymer compound of the present invention may be contained.
[0167] The ink composition contains usually a solvent in addition
to the polymer compound of the present invention, and additives
such as hole transporting materials, electron transporting
materials, light emitting materials, stabilizers, additives for
controlling viscosity and/or surface tension, and antioxidants and
the like may be contained.
[0168] The proportion of the polymer compound of the present
invention in the ink composition is usually 20 wt % to 100 wt %,
preferably 40 wt % to 100 wt % based on the total weight of the
composition excepting a solvent.
[0169] The proportion of a solvent in the ink composition is 1 wt %
to 99.9 wt %, preferably 60 wt % to 99.9 wt %, further preferably
90 wt % to 99.8 wt % based on the total weight of the ink
composition.
[0170] The viscosity of the ink composition varies depending on the
printing method, and is preferably in the range from 0.5 to 500
mPas, at 25.degree. C., and when the ink composition passes through
a discharge apparatus such as in an inkjet printing method and the
like, the viscosity is preferably in the range from 0.5 to 20 mPas,
at 25.degree. C. for preventing clogging and aviation curve in
discharging.
[0171] As the solvent used in the ink composition, those capable of
dissolving or uniformly dispersing the polymer compound of the
present invention are preferable. Exemplified as the solvent are
chlorine-based solvents such as chloroform, methylene chloride,
1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene,
o-dichlorobenzene and the like, ether solvents such as
tetrahydrofuran, dioxane and the like, aromatic hydrocarbon
solvents such as toluene, xylene, trimethylbenzene, mesitylene and
the like, aliphatic hydrocarbon solvents such as cyclohexane,
methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane,
n-nonane, n-decane and the like, ketone solvents such as acetone,
methyl ethyl ketone, cyclohexanone and the like, ester solvents
such as ethyl acetate, butyl acetate, methyl benzoate, ethyl
cellosolve acetate and the like, polyhydric alcohols such as
ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol
monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane,
propylene glycol, diethoxymethane, triethylene glycol monoethyl
ether, glycerin, 1,2-hexanediol and the like and derivatives
thereof, alcohol solvents such as methanol, ethanol, propanol,
isopropanol, cyclohexanol and the like, sulfoxide solvents such as
dimethyl sulfoxide and the like, and amide solvents such as
N-methyl-2-pyrrolidone, N,N-dimethylformamide and the like. These
organic solvents can be used singly or in combination of two or
more. Of the above-described solvents, at least one organic solvent
having a structure containing at least one benzene ring and having
a melting point of 0.degree. C. or lower and a boiling point of
100.degree. C. or higher is preferably contained.
[0172] Regarding the kind of the solvent, aromatic hydrocarbon
solvents, aliphatic hydrocarbon solvents, ester solvents and ketone
solvents are preferable from the standpoint of solubility of the
polymer compound of the present invention into an organic solvent,
uniformity in film formation, viscosity property and the like, and
toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene,
mesitylene, n-propylbenzene, i-propylbenene, n-butylbenzene,
i-butylbenzene, s-butylbenzene, anisole, ethoxybenzene,
1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene,
bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane,
n-hexylcyclohexane, methyl benzoate, 2-propylcyclohexanone,
2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone,
2-decanone and dicyclohexylketone are preferable, and at least one
of xylene, anisole, mesitylene, cyclohexylbenzene and
bicyclohexylmethyl benzoate is more preferably contained.
[0173] Of additives which can be contained in the ink composition
of the present invention, mentioned as the hole transporting layer
are polyvinylcarbazole or derivatives thereof, polysilane or
derivatives thereof, polysiloxane derivatives having an aromatic
amine at a side chain or main chain, pyrazoline derivatives,
arylamine derivatives, stilbene derivatives, triphenyldiamine
derivatives, polyaniline or derivatives thereof, polythiophene or
derivatives thereof, polypyrrole or derivatives thereof,
poly(p-phenylenevinylene) or derivatives thereof, and
poly(2,5-thienylenevinylene) or derivatives thereof.
[0174] Mentioned as the electron transporting material are
oxadiazole derivatives, anthraquinodimethane or derivatives
thereof, benzoquinone or derivatives thereof, naphthoquinone or
derivatives thereof, anthraquinone or derivatives thereof,
tetracyanoanthraquinodimethane or derivatives thereof, fluorenone
derivatives, diphenyldicyanoethylene or derivatives thereof,
diphenoquinone derivatives; metal complexes of 8-hydroxyquinoline
or derivatives thereof; polyquinoline or derivatives thereof,
polyquinoxaline or derivatives thereof, polyfluorene or derivatives
thereof.
[0175] Mentioned as the light emitting material are naphthalene
derivatives, anthracene or derivatives thereof, perylene or
derivatives thereof; coloring matters such as polymethine,
xanthene, coumarin, cyanine and the like; metal complexes of
8-hydroxyquinoline or derivatives thereof; aromatic amines,
tetraphenylcyclopentadiene or derivatives thereof,
tetraphenylbutadiene or derivatives thereof, and the like.
[0176] As the stabilizer, phenol-based antioxidants,
phosphorus-based antioxidants and the like are mentioned.
[0177] As the additives for controlling viscosity and/or surface
tension, polymer compounds of higher molecular weight (thickening
agents) for enhancing viscosity, poor solvents, compounds of lower
molecular weight for lowering viscosity, surfactants for lowering
surface tension, and the like may be appropriately combined and
used.
[0178] As the above-described polymer compound of higher molecular
weight, those which are soluble in the same solvent as for the
polymer compound of the present invention and do not disturb light
emission and charge transportation are advantageous. For example,
polystyrene and polymethyl methacrylate of higher molecular weight,
or polymer compounds of the present invention having higher
molecular weight, and the like can be used. The weight average
molecular weight is preferably 500000 or more, and more preferably
1000000 or more. A poor solvent can also be used as a thickening
agent. That is, viscosity can be enhanced by adding a small amount
of poor solvent for solid components in a solution. When a poor
solvent is added for this purpose, the kind and addition amount of
the solvent may be advantageously selected so as not to cause
deposition of solid components in a solution. When stability in
preservation is also taken into consideration, the amount of a poor
solvent is preferably 50 wt % or less, further preferably 30 wt %
or less based on the whole solution.
[0179] As the antioxidant, those which are soluble in the same
solvent as for the polymer compound of the present invention and
dot not disturb light emission and charge transportation are
advantageous, and exemplified are phenol-based antioxidants,
phosphorus-based antioxidants and the like. By using the
antioxidant, preservation stability of the polymer compound of the
present invention and the solvent can be improved.
[0180] From the standpoint of solubility of the polymer compound of
the present invention into a solvent, the difference between
solubility parameter of the solvent and solubility parameter of the
polymer compound is preferably 10 or less, more preferably 7 or
less.
[0181] The solubility parameter of the solvent and the solubility
parameter of the polymer compound of the present invention can be
measured by a method described in "Solvent Handbook (Kodansha Ltd.
Publishers, 1976)".
[0182] The polymer compounds of the present invention to be
contained in an ink composition may be used singly or in
combination of two or more, and polymer compounds other than the
polymer compound of the present invention may be contained in a
range not deteriorating device properties and the like.
[0183] The thickness of a light emitting layer has an optimum value
varying depending on a material to be used and may be
advantageously selected to give suitable driving voltage and light
emitting efficiency, and is, for example, from 1 nm to 1 .mu.m,
preferably from 2 nm to 500 nm, further preferably from 5 nm to 200
nm.
[0184] When the polymer LED of the present invention has a hole
transporting layer, as the hole transporting materials used, there
are exemplified polyvinylcarbazole or derivatives thereof,
polysilane or derivatives thereof, polysiloxane derivatives having
an aromatic amine in the side chain or the main chain, pyrazoline
derivatives, arylamine derivatives, stilbene derivatives,
triphenyldiamine derivatives, polyaniline or derivatives thereof,
polythiophene or derivatives thereof, polypyrrole or derivatives
thereof, poly(p-phenylenevinylene) or derivatives thereof,
poly(2,5-thienylenevinylene) or derivatives thereof, or the
like.
[0185] Specific examples of the hole transporting material include
those described in JP-A Nos. 63-70257, 63-175860, 2-135359,
2-135361, 2-209988, 3-37992 and 3-152184.
[0186] Among them, as the hole transporting materials used in the
hole transporting layer, preferable are polymer hole transporting
materials such as polyvinylcarbazole or derivatives thereof,
polysilane or derivatives thereof, polysiloxane derivatives having
an aromatic amine compound group in the side chain or the main
chain, polyaniline or derivatives thereof, polythiophene or
derivatives thereof, poly(p-phenylenevinylene) or derivatives
thereof, poly(2,5-thienylenevinylene) or derivatives thereof, or
the like, and further preferable are polyvinylcarbazole or
derivatives thereof, polysilane or derivatives thereof and
polysiloxane derivatives having an aromatic amine compound group in
the side chain or the main chain. In the case of a hole
transporting material having lower molecular weight, it is
preferably dispersed in a polymer binder for use.
[0187] Polyvinylcarbazole or derivatives thereof are obtained, for
example, by cation polymerization or radical polymerization from a
vinyl monomer.
[0188] As the polysilane or derivatives thereof, there are
exemplified compounds described in Chem. Rev., 89, 1359 (1989) and
GB 2300196 published specification, and the like. For synthesis,
methods described in them can be used, and a Kipping method can be
suitably used particularly.
[0189] As the polysiloxane or derivatives thereof, those having the
structure of the above-described hole transporting material having
lower molecular weight in the side chain or main chain, since the
siloxane skeleton structure has poor hole transporting property.
Particularly, there are exemplified those having an aromatic amine
having hole transporting property in the side chain or main
chain.
[0190] The method for forming a hole transporting layer is not
restricted, and in the case of a hole transporting layer having
lower molecular weight, a method in which the layer is formed from
a mixed solution with a polymer binder is exemplified. In the case
of a polymer hole transporting material, a method in which the
layer is formed from a solution is exemplified.
[0191] The solvent used for the film forming from a solution is not
particularly restricted providing it can dissolve a hole
transporting material. As the solvent, there are exemplified
chlorine solvents such as chloroform, methylene chloride,
dichloroethane and the like, ether solvents such as tetrahydrofuran
and the like, aromatic hydrocarbon solvents such as toluene, xylene
and the like, ketone solvents such as acetone, methyl ethyl ketone
and the like, and ester solvents such as ethyl acetate, butyl
acetate, ethylcellosolve acetate and the like.
[0192] As the film forming method from a solution, there can be
used coating methods such as a spin coating method, casting method,
micro gravure coating method, gravure coating method, bar coating
method, roll coating method, wire bar coating method, dip coating
method, spray coating method, screen printing method, flexo
printing method, offset printing method, inkjet printing method and
the like, from a solution.
[0193] The polymer binder mixed is preferably that does not disturb
charge transport extremely, and that does not have strong
absorption of a visible light is suitably used. As such polymer
binder, polycarbonate, polyacrylate, poly(methyl acrylate),
poly(methyl methacrylate), polystyrene, poly(vinyl chloride),
polysiloxane and the like are exemplified.
[0194] Regarding the thickness of the hole transporting layer, the
optimum value differs depending on material used, and may properly
be selected so that the driving voltage and the light emitting
efficiency become optimum values, and at least a thickness at which
no pin hole is produced is necessary, and too large thickness is
not preferable since the driving voltage of the device increases.
Therefore, the thickness of the hole transporting layer is, for
example, from 1 nm to 1 .mu.m, preferably from 2 nm to 500 nm,
further preferably from 5 nm to 200 nm.
[0195] When the polymer LED of the present invention has an
electron transporting layer, known compounds are used as the
electron transporting materials, and there are exemplified
oxadiazole derivatives, anthraquinodimethane or derivatives
thereof, benzoquinone or derivatives thereof, naphthoquinone or
derivatives thereof, anthraquinone or derivatives thereof,
tetracyanoanthraquinodimethane or derivatives thereof, fluorenone
derivatives, diphenyldicyanoethylene or derivatives thereof,
diphenoquinoline derivatives, or metal complexes of
8-hydroxyquinoline or derivatives thereof, polyquinoline and
derivatives thereof, polyquinoxaline and derivatives thereof,
polyfluorene or derivatives thereof, and the like.
[0196] Specifically, there are exemplified those described in JP-A
Nos. 63-70257, 63-175860, 2-135359, 2-135361, 2-209988, 3-37992 and
3-152184.
[0197] Among them, oxadiazole derivatives, benzoquinone or
derivatives thereof, anthraquinone or derivatives thereof, or metal
complexes of 8-hydroxyquinoline or derivatives thereof,
polyquinoline and derivatives thereof, polyquinoxaline and
derivatives thereof, polyfluorene or derivatives thereof are
preferable, and
2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole, benzoquinone,
anthraquinone, tris(8-quinolinol)aluminum and polyquinoline are
further preferable.
[0198] The method for forming the electron transporting layer is
not particularly restricted, and in the case of an electron
transporting material having lower molecular weight, a vapor
deposition method from a powder, or a method of film-forming from a
solution or melted state is exemplified, and in the case of a
polymer electron transporting material, a method of film-forming
from a solution or melted state is exemplified, respectively.
[0199] The solvent used in the film-forming from a solution is not
particularly restricted provided it can dissolve electron
transporting materials and/or polymer binders. As the solvent,
there are exemplified chlorine solvents such as chloroform,
methylene chloride, dichloroethane and the like, ether solvents
such as tetrahydrofuran and the like, aromatic hydrocarbon solvents
such as toluene, xylene and the like, ketone solvents such as
acetone, methyl ethyl ketone and the like, and ester solvents such
as ethyl acetate, butyl acetate, ethylcellosolve acetate and the
like.
[0200] As the film-forming method from a solution or melted state,
there can be used coating methods such as a spin coating method,
casting method, micro gravure coating method, gravure coating
method, bar coating method, roll coating method, wire bar coating
method, dip coating method, spray coating method, screen printing
method, flexo printing method, offset printing method, inkjet
printing method and the like.
[0201] The polymer binder to be mixed is preferably that which does
not extremely disturb a charge transport property, and that does
not have strong absorption of a visible light is suitably used. As
such polymer binder, poly(N-vinylcarbazole), polyaniline or
derivatives thereof, polythiophene or derivatives thereof,
poly(p-phenylene vinylene) or derivatives thereof,
poly(2,5-thienylene vinylene) or derivatives thereof,
polycarbonate, polyacrylate, poly(methyl acrylate), poly(methyl
methacrylate), polystyrene, poly(vinyl chloride), polysiloxane and
the like are exemplified.
[0202] Regarding the thickness of the electron transporting layer,
the optimum value differs depending on material used, and may
properly be selected so that the driving voltage and the light
emitting efficiency become optimum values, and at least a thickness
at which no pin hole is produced is necessary, and too large
thickness is not preferable since the driving voltage of the device
increases. Therefore, the thickness of the electron transporting
layer is, for example, from 1 nm to 1 .mu.m, preferably from 2 nm
to 500 nm, further preferably from 5 nm to 200 nm.
[0203] The substrate forming the polymer LED of the present
invention may preferably be that does not change in forming an
electrode and layers of organic materials, and there are
exemplified glass, plastics, polymer film, silicon substrates and
the like. In the case of a opaque substrate, it is preferable that
the opposite electrode is transparent or semitransparent.
[0204] Usually, at least one of the electrodes consisting of an
anode and a cathode, is transparent or semitransparent. It is
preferable that the anode is transparent or semitransparent.
[0205] As the material of this anode, electron conductive metal
oxide films, semitransparent metal thin films and the like are
used. Specifically, there are used indium oxide, zinc oxide, tin
oxide, and composition thereof, i.e. indium/tin/oxide (ITO), and
films (NESA and the like) fabricated by using an electron
conductive glass composed of indium/zinc/oxide, and the like, and
gold, platinum, silver, copper and the like. Among them, ITO,
indium/zinc/oxide, tin oxide are preferable. As the fabricating
method, a vacuum vapor deposition method, sputtering method, ion
plating method, plating method and the like are used. As the anode,
there may also be used organic transparent conducting films such as
polyaniline or derivatives thereof, polythiophene or derivatives
thereof and the like.
[0206] The thickness of the anode can be appropriately selected
while considering transmission of a light and electric
conductivity, and for example, from 10 nm to 10 .mu.m, preferably
from 20 nm to 1 .mu.m, further preferably from 50 nm to 500 nm.
[0207] Further, for easy charge injection, there may be provided on
the anode a layer comprising a phthalocyanine derivative conducting
polymers, carbon and the like, or a layer having an average film
thickness of 2 nm or less comprising a metal oxide, metal fluoride,
organic insulating material and the like.
[0208] As the material of a cathode used in the polymer LED of the
present invention, that having lower work function is preferable.
For example, there are used metals such as lithium, sodium,
potassium, rubidium, cesium, beryllium, magnesium, calcium,
strontium, barium, aluminum, scandium, vanadium, zinc, yttrium,
indium, cerium, samarium, europium, terbium, ytterbium and the
like, or alloys comprising two of more of them, or alloys
comprising one or more of them with one or more of gold, silver,
platinum, copper, manganese, titanium, cobalt, nickel, tungsten and
tin, graphite or graphite intercalation compounds and the like.
Examples of alloys include a magnesium-silver alloy,
magnesium-indium alloy, magnesium-aluminum alloy, indium-silver
alloy, lithium-aluminum alloy, lithium-magnesium alloy,
lithium-indium alloy, calcium-aluminum alloy and the like. The
cathode may be formed into a laminated structure of two or more
layers.
[0209] The thickness of the cathode can be appropriately selected
while considering transmission of a light and electric
conductivity, and for example, from 10 nm to 10 .mu.m, preferably
from 20 nm to 1 .mu.m, further preferably from 50 nm to 500 nm.
[0210] As the method for fabricating a cathode, there are used a
vacuum vapor deposition method, sputtering method, lamination
method in which a metal thin film is adhered under heat and
pressure, and the like. Further, there may also be provided,
between a cathode and an organic layer, a layer comprising an
conducting polymer, or a layer having an average film thickness of
2 nm or less comprising a metal oxide, metal fluoride, organic
insulation material and the like, and after fabrication of the
cathode, a protective layer may also be provided which protects the
polymer LED. For stable use of the polymer LED for a long period of
time, it is preferable to provide a protective layer and/or
protective cover for protection of the device in order to prevent
it from outside damage.
[0211] As the protective layer, there can be used a polymeric
compound, metal oxide, metal fluoride, metal borate and the like.
As the protective cover, there can be used a glass plate, a plastic
plate the surface of which has been subjected to
lower-water-permeation treatment, and the like, and there is
suitably used a method in which the cover is pasted with an device
substrate by a thermosetting resin or light-curing resin for
sealing. If space is maintained using a spacer, it is easy to
prevent an device from being injured. If an inner gas such as
nitrogen and argon is sealed in this space, it is possible to
prevent oxidation of a cathode, and further, by placing a desiccant
such as barium oxide and the like in the above-described space, it
is easy to suppress the damage of an device by moisture adhered in
the production process. Among them, any one means or more are
preferably adopted.
[0212] The polymer LED of the present invention can be used for a
flat light source, a segment display, a dot matrix display, and a
liquid crystal display as a back light, etc.
[0213] For obtaining light emission in plane form using the polymer
LED of the present invention, an anode and a cathode in the plane
form may properly be placed so that they are laminated each other.
Further, for obtaining light emission in pattern form, there is a
method in which a mask with a window in pattern form is placed on
the above-described plane light emitting device, a method in which
an organic layer in non-light emission part is formed to obtain
extremely large thickness providing substantial non-light emission,
and a method in which any one of an anode or a cathode, or both of
them are formed in the pattern. By forming a pattern by any of
these methods and by placing some electrodes so that independent
on/off is possible, there is obtained a display device of segment
type which can display digits, letters, simple marks and the like.
Further, for forming a dot matrix device, it may be advantageous
that anodes and cathodes are made in the form of stripes and placed
so that they cross at right angles. By a method in which a
plurality of kinds of polymeric compounds emitting different colors
of lights are placed separately or a method in which a color filter
or luminescence converting filter is used, area color displays and
multi color displays are obtained. A dot matrix display can be
driven by passive driving, or by active driving combined with TFT
and the like. These display devices can be used as a display of a
computer, television, portable terminal, portable telephone, car
navigation, view finder of a video camera, and the like.
[0214] Further, the above-described light emitting device in plane
form is a thin self-light-emitting one, and can be suitably used as
a flat light source for back-light of a liquid crystal display, or
as a flat light source for illumination. Further, if a flexible
plate is used, it can also be used as a curved light source or a
display.
[0215] Examples are shown below for illustrating the present
invention further in detail, however, the present invention is not
limited to them.
[0216] Here, as the number average molecular weight and weight
average molecular weight, polystyrene reduced number average
molecular weight and polystyrene reduced weight average molecular
weight were measured by gel permeation chromatography (GPC) using
tetrahydrofuran as a solvent.
Synthesis Example 1
Synthesis of Monomer (2)
##STR00055##
[0217] (Synthesis of Compound D)
##STR00056##
[0219] Under an inert atmosphere, into a 300 ml three-necked flask
was added 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35
mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium
carbonate, 36 mol of toluene and 36 mol of ion exchanged water, and
argon was bubbled through the mixture for 20 minutes while stirring
at room temperature. Subsequently, 16.8 mg (0.15 mmol) of
tetrakis(triphenylphosphine) palladium was added, and further,
argon was bubbled through the mixture for 10 minutes while stirring
at room temperature. The mixture was heated up to 100.degree. C.
and reacted for 25 hours. The reaction mixture was cooled down to
room temperature, the organic layer was extracted with toluene,
dried over sodium sulfate, then, the solvent was distilled off.
Purification was performed by a silica gel column using
toluene:cyclohexane=1:2 mixed solvent as a development solvent, to
obtain 5.18 g (yield: 86%) of compound D as a white crystal.
.sup.1H-NMR (300 MHz/CDCl.sub.3):
[0220] .delta. 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12
(dd, 2H), 9.63 (s, 1H)
[0221] MS (APCI (+)): (M+H).sup.+ 233
(Synthesis of Compound E)
##STR00057##
[0223] Under an inert atmosphere, into a 300 ml three-necked flask
was added 8.00 g (34.4 mmol) of compound D and 46 mol of dehydrated
THF, and the mixture was cooled down to -78.degree. C.
Subsequently, 52 ml of n-octylmagnesium bromide (1.0 mol/l THF
solution) was dropped over 30 minutes. After completion of
dropping, the mixture was heated up to 0.degree. C., stirred for 1
hour, then, heated up to room temperature and stirred for 45
minutes. The flask was immersed in an ice bath and 20 ml of 1 N
hydrochloric acid was added to stop the reaction, the organic layer
was extracted with ethyl acetate, and dried over sodium sulfate.
Then solvent was distilled off, then, purification was performed by
a silica gel column using toluene:hexane=10:1 mixed solvent as a
development solvent, to obtain 7.64 g (yield: 64%) of compound E as
a pale yellow oil. Though two peaks were observed in HPLC
measurement, equal mass numbers were obtained in LC-MS measurement,
thus, the product was judged to be a mixture of isomers.
(Synthesis of Compound F)
##STR00058##
[0225] Under an inert atmosphere, into a 500 ml three-necked flask
was added 5.00 g (14.4 mmol) of compound E (mixture of isomers) and
74 mol of dehydrated dichloromethane, and the mixture was stirred
at room temperature to cause dissolution thereof. Subsequently, an
etherate complex of boron trifluoride was dropped at room
temperature over 1 hour, and after completion of dropping, the
mixture was stirred at room temperature for 4 hours. 125 ml of
ethanol was added slowly while stirring, and when heat generation
disappeared, the organic layer was extracted with chloroform,
washed with water twice, and dried over magnesium sulfate. Then
solvent was distilled off, then, purification was performed by a
silica gel column using hexane as a development solvent, to obtain
3.22 g (yield: 68%) of compound F as a colorless oil.
[0226] .sup.1H-NMR (300 MHz/CDCl.sub.3):
[0227] .delta. 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05
(t, 1H), 7.35 (dd, 1H), 7.46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82
(d, 1H), 7.94 (d, 1H), 8.35 (d, 1H), 8.75 (d, 1H)
[0228] MS (APCI (+)): (M+H).sup.+ 329
(Synthesis of Compound G)
##STR00059##
[0230] Under an inert atmosphere, into a 200 ml three-necked flask
was added 20 ml of ion exchanged water, and 18.9 g (0.47 mol) of
sodium hydroxide was added portionwise and dissolved while
stirring. The aqueous solution was cooled down to room temperature,
then, 20 ml of toluene, 5.17 g (15.7 mmol) of compound F and 1.52 g
(4.72 mmol) of tributyl ammonium bromide were added and the mixture
was heated up to 50.degree. C. n-octyl bromide was dropped, and
after completion of dropping, the mixture was reacted for 9 hours
at 50.degree. C. After completion of the reaction, the organic
layer was extracted with toluene, washed with water twice, and
dried over sodium sulfate. Purification was performed by a silica
gel column using hexane as a development solvent, to obtain 5.13 g
(yield: 74%) of compound G as a yellow oil.
[0231] .sup.1H-NMR (300 MHz/CDCl.sub.3):
[0232] .delta. 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05
(t, 4 H), 7.34 (d, 1H), 7.40-7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1
H), 7.94 (d, 1H), 8.31 (d, 1H), 8.75 (d, 1H)
[0233] MS (APCI (+)): (M+H).sup.+ 441
(Synthesis of Compound H)
##STR00060##
[0235] Under an air atmosphere, into a 50 ml three-necked flask was
added 4.00 g (9.08 mmol) of compound G and 57 ml of acetic
acid:dichloromethane=1:1 mixed solvent, and the mixture was stirred
at room temperature to cause dissolution thereof. Subsequently,
7.79 g (20.0 mmol) of benzyltrimethyl ammonium tribromide was added
and zinc chloride was added until complete dissolution of
benzyltrimethyl ammonium tribromide while stirring. The mixture was
stirred at room temperature for 20 hours, then, 10 ml of a 5%
sodium hydrogen sulfite aqueous solution was added to stop the
reaction, the organic layer was extracted with chloroform, washed
twice with a potassium carbonate aqueous solution, and dried over
sodium sulfate. Purification was performed twice by a flash column
using hexane as a development solvent, then, recrystallization was
performed with ethanol:hexane=1:1, then, with 10:1 mixed solvent,
to obtain 4.13 g (yield: 76%) of compound H as a white crystal.
[0236] .sup.1H-NMR (300 MHz/CDCl.sub.3):
[0237] .delta. 0.60 (m, 2H), 0.91 (t, 6H), 1.01-1.38 (m, 22H), 2.09
(t, 4H), 7.62-7.75 (m, 3H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d,
1H), 8.72 (d, 1H)
[0238] MS (APPI (+)): (M+H).sup.+ 598
[0239] Here, the resultant compound H is called monomer (2).
Example 1
Synthesis of Polymer Compound 1
##STR00061##
[0241] 0.07 g of monomer (1), 0.81 g of monomer (2) and 0.63 g of
2,2'-bipyridyl were charged into a reaction vessel, then, an
atmosphere in the reaction system was purged with a nitrogen gas.
To this was added 50 g of tetrahydrofuran (dehydrated solvent)
deaerated by bubbling with an argon gas previously. Next, to this
mixed solution was added 1.1 g of bis(1.5-cyclooctadiene)nickel(0),
and the mixture was stirred at room temperature for about 10
minutes, then, heated up and reacted at 60.degree. C. for 3 hours.
The reaction was carried out in a nitrogen atmosphere.
[0242] This reaction liquid was cooled, then, ethanol 40 ml/ion
exchanged water 40 ml mixed solution was added, and the mixture was
stirred for about 1 hour. This solution was allowed to stand still
over night at room temperature, then, the produced precipitate was
recovered by filtration. Then, this precipitate was dried under
reduced pressure, then, dissolved in toluene. Insoluble materials
were removed by filtrating this toluene solution. Next, this
toluene solution was washed with 1 N hydrochloric acid, then,
allowed to stand still, and liquid separation was caused and the
toluene solution was recovered. Next, this toluene solution was
washed with ca. 3% ammonia water, then, allowed to stand still, and
liquid separation was caused and the toluene solution was
recovered. Next, this toluene solution was washed with ion
exchanged water, then, allowed to stand still, and liquid
separation was caused and the toluene solution was recovered. Next,
this toluene solution was poured into methanol, and purified by
re-precipitation. The produced precipitate was recovered, and
washed with ethanol, then, this was dried under reduced pressure,
to obtain 0.13 g of a polymer. The resulting polymer is called
polymer compound 1.
[0243] This polymer compound 1 had a polystyrene reduced number
average molecular weight of 6.5.times.10.sup.4 and a polystyrene
reduced weight average molecular weight of 3.3.times.10.sup.5. The
structure of a repeating unit contained in polymer compound 1
estimated from charging is shown below.
##STR00062##
Example 2
Synthesis of Polymer Compound 2
[0244] 0.07 g of monomer (1), 1.0 g of
N,N'-(4-tert-butyl-2,6-dimethylphenyl)-N,N'-(4-bromophenyl)-1,4-phenylene-
diamine and 0.63 g of 2,2'-bipyridyl were charged into a reaction
vessel, then, an atmosphere in the reaction system was purged with
a nitrogen gas. To this was added 50 g of tetrahydrofuran
(dehydrated solvent) deaerated by bubbling with an argon gas
previously. Next, to this mixed solution was added 1.1 g of
bis(1.5-cyclooctadiene)nickel(0), and the mixture was stirred at
room temperature for about 10 minutes, then, heated up and reacted
at 60.degree. C. for 3 hours. The reaction was carried out in a
nitrogen atmosphere.
[0245] This reaction liquid was cooled, then, methanol 40 ml/ion
exchanged water 40 ml mixed solution was added, and the mixture was
stirred for about 1 hour. This solution was allowed to stand still
over night at room temperature, then, the produced precipitate was
recovered by filtration. Then, this precipitate was dried under
reduced pressure, then, dissolved in toluene. Insoluble materials
were removed by filtrating this toluene solution. Next, this
toluene solution was purified by passing through a column filled
with alumina. Then, this toluene solution was washed with 1 N
hydrochloric acid, then, allowed to standstill, and liquid
separation was caused and the toluene solution was recovered. Next,
this toluene solution was washed with ca. 3% ammonia water, then,
allowed to standstill, and liquid separation was caused and the
toluene solution was recovered. Next, this toluene solution was
washed with ion exchanged water, then, allowed to stand still, and
liquid separation was caused and the toluene solution was
recovered. Next, this toluene solution was poured into methanol,
and purified by re-precipitation. The produced precipitate was
recovered, and washed with ethanol, then, this was dried under
reduced pressure, to obtain 0.14 g of a polymer. The resulting
polymer is called polymer compound 2.
[0246] This polymer compound 2 had a polystyrene reduced number
average molecular weight of 4.8.times.10.sup.3 and a polystyrene
reduced weight average molecular weight of 5.8.times.10.sup.3. The
structure of a repeating unit contained in polymer compound 2
estimated from charging is shown below.
##STR00063##
Example 3
Synthesis of Polymer Compound 3
[0247] 0.035 g of monomer (1), 0.90 g of monomer (2) and 0.63 g of
2,2'-bipyridyl were charged into a reaction vessel, then, an
atmosphere in the reaction system was purged with a nitrogen gas.
To this was added 60 g of tetrahydrofuran (dehydrated solvent)
deaerated by bubbling with an argon gas previously. Next, to this
mixed solution was added 1.1 g of bis(1.5-cyclooctadiene)nickel(0),
and the mixture was stirred at room temperature for about 10
minutes, then, heated up and reacted at 60.degree. C. for 3 hours.
The reaction was carried out in a nitrogen atmosphere.
[0248] This reaction liquid was cooled, then, methanol 50 ml/ion
exchanged water 50 ml mixed solution was added, and the mixture was
stirred for about 1 hour. This solution was allowed to stand still
over night at room temperature, then, the produced precipitate was
recovered by filtration. Then, this precipitate was dried under
reduced pressure, then, dissolved in toluene. Insoluble materials
were removed by filtrating this toluene solution. Next, this
toluene solution was purified by passing through a column filled
with alumina. Then, this toluene solution was washed with 1 N
hydrochloric acid, then, allowed to stand still, and liquid
separation was caused and the toluene solution was recovered. Next,
this toluene solution was washed with ca. 3% ammonia water, then,
allowed to stand still, and liquid separation was caused and the
toluene solution was recovered. Next, this toluene solution was
washed with ion exchanged water, then, allowed to stand still, and
liquid separation was caused and the toluene solution was
recovered. Next, this toluene solution was poured into methanol,
and purified by re-precipitation. The produced precipitate was
recovered, and washed with ethanol, then, this was dried under
reduced pressure, to obtain 0.3 g of a polymer. The resulting
polymer is called polymer compound 3.
[0249] This polymer compound 3 had a polystyrene reduced number
average molecular weight of 8.9.times.10.sup.4 and a polystyrene
reduced weight average molecular weight of 4.9.times.10.sup.5. The
structure of a repeating unit contained in polymer compound 3
estimated from charging is shown below.
##STR00064##
Example 4
Synthesis of Polymer Compound 4
[0250] 0.07 g of monomer (1), 0.59 g of
2,7-dibromo-9,9-dioctylfluorene, 0.125 g of
bromo-9,9-diisopentylfluorene and 0.63 g of 2,2'-bipyridyl were
charged into a reaction vessel, then, an atmosphere in the reaction
system was purged with a nitrogen gas. To this was added 60 g of
tetrahydrofuran (dehydrated solvent) deaerated by bubbling with an
argon gas previously. Next, to this mixed solution was added 1.1 g
of bis(1.5-cyclooctadiene)nickel(0), and the mixture was stirred at
room temperature for about 10 minutes, then, reacted at 60.degree.
C. for 3 hours. The reaction was carried out in a nitrogen
atmosphere.
[0251] After the reaction, this solution was cooled, then, into
this solution was poured methanol 50 ml/ion exchanged water 50 ml
mixed solvent, and the mixture was stirred for about 1 hour. Then,
the produced precipitate was recovered by filtration. This
precipitate was washed with methanol, then, dried under reduced
pressure. Then, this precipitate was dissolved in toluene.
Insoluble materials were removed by filtrating this toluene
solution, then, this toluene solution was washed with 1 N
hydrochloric acid. The solution was allowed to stand still, and
liquid separation was caused, then, this toluene solution was
washed with ca. 3% ammonia water. The solution was allowed to stand
still, and liquid separation was caused, then, this toluene
solution was washed with ion exchanged water. The solution was
allowed to stand still, and liquid separation was caused, to obtain
a purified toluene solution. Next, this toluene solution was poured
into methanol, and purified by re-precipitation. The resultant
precipitate was dried under reduced pressure, to obtain 0.18 g of a
polymer. This polymer is called polymer compound 4.
[0252] This polymer compound 4 had a polystyrene reduced number
average molecular weight of 9.8.times.10.sup.4 and a polystyrene
reduced weight average molecular weight of 5.7.times.10.sup.5.
[0253] The structure of a repeating unit contained in polymer
compound 4 estimated from charging is shown below.
##STR00065##
Example 5
Measurement of Absorption Spectrum, Fluorescent Spectrum
[0254] Polymer compounds 1 to 4 could be dissolved in chloroform.
Its 0.2% chloroform solution was spin-coated on a quartz plate to
form a thin film of the polymer compound. The fluorescent spectrum
of this thin film was measured by JASCO FP-6500 spectrofluorometer.
The fluorescent peak wavelengths of polymer compounds 1 to 4 are
shown in Table 1.
TABLE-US-00001 TABLE 1 fluorescent peak wavelength polymer compound
(nm) 1 474 2 496 3 451 4 486
Example 6
Manufacturing and Evaluation of Device
[0255] On a glass substrate carrying thereon an ITO film with a
thickness of 150 nm formed by a sputtering method, a solution
prepared by filtrating a suspension of
poly(3,4)ethylenedioxythiophene/polystyrenesulfonic acid
(manufactured by Bayer, BaytronP AI4083) through a 0.2 .mu.m
membrane filter was spin-coated to form a thin film with a
thickness of 70 nm, and dried on a hot plate at 200.degree. C. for
10 minutes. Next, a 1.5 wt % toluene solution of polymer compound 4
was spin-coated to form a film with a thickness of 120 nm. Further,
this was dried at 80.degree. C. under reduced pressure for 1 hour,
then, lithium fluoride was vapor-deposited with a thickness of
about 4 nm, then, as a cathode, calcium was vapor-deposited with a
thickness of about 5 nm and then aluminum was vapor-deposited with
a thickness of about 70 nm, to manufacture a polymer LED. After the
degree of vacuum reached 1.times.10.sup.-4 Pa or less,
vapor-deposition of a metal was initiated.
[0256] By applying voltage on the resultant device, EL light
emission showing a peak at 500 nm was obtained from this device.
C.I.E. color coordinate values at 100 cd/m.sup.2 were x=0.23 and
y=0.49, and the emitted color was blue green. The intensity of EL
light emission was approximately in proportion to current density.
This device showed initiation of light emission from 9.1 V, and the
maximum light emitting efficiency was 0.26 cd/A.
Synthesis Example 2
Synthesis of Monomer (3)
##STR00066##
[0258] To 4-bromophenol was reacted 1,5-diiodopentane in the
presence of an alkali, to obtain 1-(1-iodopentyloxy)-4-bromobenzene
{compound (A)}.
##STR00067##
[0259] 9.0 g of compound (A), 1.25 g of quinacridone and 0.91 g of
benzyltriethylammonium chloride were dissolved in 70 g of
1,2-dichlorobenzene. To this solution was added 60 g of a 40%
sodium hydroxide aqueous solution and the mixture was stirred
vigorously, and reacted at 110.degree. C. for 25 hours. The
reaction was carried out in a nitrogen atmosphere.
[0260] After the reaction, this reaction solution was cooled. This
was allowed to stand still, to find liquid separation, thus, a
1,2-dichlorobenzene solution was recovered by liquid separation. To
this 1,2-dichlorobenzene solution was added toluene, then, this
solution was washed with water. After water washing, the oil layer
was recovered by liquid separation, and allowed to stand still, to
find production of a precipitate. Next, this solution was filtrated
to recover the produced precipitate.
[0261] Next, this precipitate was washed with ethanol, and dried
under reduced pressure, then, dissolved in chloroform. This
solution was filtrated to remove insoluble materials, then,
purified by using a column filled with alumina.
[0262] The resultant solution was poured into methanol, and
purified by re-precipitation. Then, the produced precipitate was
recovered by a filtration operation. This precipitate was dried
under reduced pressure to obtain 100 mg of monomer (3).
[0263] .sup.1H-NMR (300 MHz/CDCl.sub.3):
[0264] .delta. 1.76-2.15 (12H), 4.01 (4H), 4.56 (4H), 6.77-6.82
(4H), 7.25-7.79 (10H), 8.56-8.77 (4H)
[0265] MS (APCI (+)): (M+H).sup.+ 795
Example 7
Synthesis of Polymer Compound (5)
[0266] 15 mg of monomer (3), 720 mg of monomer (2) and 0.53 g of
2,2'-bipyridyl were dissolved in 50 g of tetrahydrofuran
(dehydrated), then, an atmosphere in the system was purged with a
nitrogen gas by bubbling a nitrogen gas. To this solution was added
0.94 g of bis(1.5-cyclooctadiene)nickel (0) {Ni(COD).sub.2}, and
the mixture was stirred at room temperature for 10 minutes, then,
heated up and reacted at 60.degree. C. for 3 hours. The reaction
was carried out in a nitrogen atmosphere.
[0267] This reaction liquid was cooled, then, to this was added
methanol 40 ml/ion exchanged water 40 ml mixed solution, and the
mixture was stirred for about 1 hour. Then, the produced
precipitate was recovered by filtration. Then, this precipitate was
dried under reduced pressure, then, dissolved in toluene. Insoluble
materials were removed by filtrating this toluene solution. Then,
this toluene solution was purified by passing through a column
filled with alumina. Then, this toluene solution was washed with 1
N hydrochloric acid, then, allowed to stand still, and liquid
separation was caused and the toluene solution was recovered. Next,
this toluene solution was washed with ca. 3% ammonia water, then,
allowed to standstill, and liquid separation was caused and the
toluene solution was recovered. Next, this toluene solution was
washed with ion exchanged water, then, allowed to stand still, and
liquid separation was caused and the toluene solution was
recovered. Next, this toluene solution was poured into methanol,
and purified by re-precipitation. The produced precipitate was
recovered, and washed with ethanol, then, this precipitate was
dried under reduced pressure, to obtain 0.16 g of a polymer. The
resultant polymer is called polymer compound (5).
[0268] This polymer compound (5) had a polystyrene reduced number
average molecular weight of 5.2.times.10.sup.4 and a polystyrene
reduced weight average molecular weight of 2.3.times.10.sup.5. The
structure of a repeating unit contained in polymer compound (5)
estimated from charging is shown below.
##STR00068##
Comparative Example 1
Synthesis of Polymer Compound (6)
[0269] A polymer was obtained in the same manner as in Example 7
excepting that monomer (3) was not used. The resultant polymer is
called polymer compound (6).
[0270] This polymer compound (6) had a polystyrene reduced number
average molecular weight of 8.2.times.10.sup.4 and a polystyrene
reduced weight average molecular weight of 2.5.times.10.sup.5. The
structure of a repeating unit contained in polymer compound (6)
estimated from charging is shown below.
##STR00069##
Example 8
Measurement of Absorption Spectrum, Fluorescent Spectrum
[0271] Polymer compounds (5) and (6) could be dissolved in toluene
easily. Its 0.8% toluene solution was spin-coated on a quartz plate
to form a thin film of the polymer compound. The fluorescent
spectrum of this thin film was measured by JASCO FP-6500
spectrofluorometer.
[0272] The fluorescent peak wavelength of polymer compounds (5) was
524 nm and the fluorescent peak wavelength of polymer compounds (6)
was 450 nm
Example 9
Manufacturing and Evaluation of Device
[0273] On a glass substrate carrying thereon an ITO film with a
thickness of 150 nm formed by a sputtering method, a solution
prepared by filtrating a suspension of
poly(3,4)ethylenedioxythiophene/polystyrenesulfonic acid
(manufactured by Bayer, BaytronP AI4083) through a 0.2 .mu.m
membrane filter was spin-coated to form a thin film with a
thickness of 70 nm, and dried on a hot plate at 200.degree. C. for
10 minutes. Next, a 1.5 wt % toluene solution of polymer compound
(5) was spin-coated to form a film with a thickness of 75 nm.
Further, this was dried at 80.degree. C. under reduced pressure for
1 hour, then, lithium fluoride was vapor-deposited with a thickness
of about 4 nm, then, as a cathode, calcium was vapor-deposited with
a thickness of about 5 nm, then, aluminum was vapor-deposited with
a thickness of about 80 nm, to manufacture a polymer LED. After the
degree of vacuum reached 1.times.10.sup.-4 Pa or less,
vapor-deposition of a metal was initiated.
[0274] By applying voltage on the resultant device, EL light
emission showing a peak at 525 nm was obtained from this device.
C.I.E. color coordinate values at 100 cd/m.sup.2 were x=0.35 and
y=0.59, and the emitted color was green. The intensity of EL light
emission was approximately in proportion to current density. This
device showed initiation of light emission from 5.6 V, and the
maximum light emitting efficiency was 0.91 cd/A.
Comparative Example 2
Manufacturing and Evaluation of Device
[0275] An EL device was manufactured in the same manner as in
Example 9 excepting that polymer compound (6) was used instead of
polymer compound (5).
[0276] By applying voltage on the resultant device, EL light
emission showing a peak at 460 nm was obtained from this device.
C.I.E. color coordinate values at 100 cd/m.sup.2 were x=0.15 and
y=0.16, and the emitted color was blue. The intensity of EL light
emission was approximately in proportion to current density. This
device showed initiation of light emission from 3.6 V, and the
maximum light emitting efficiency was 0.4 cd/A.
INDUSTRIAL APPLICABILITY
[0277] The polymer compound of the present invention is useful as a
light emitting material. The polymer light emitting device using
this polymer compound shows high performance, and can be used as an
apparatus such as a sheet light source as back light, flat panel
display or the like.
* * * * *