U.S. patent application number 10/309101 was filed with the patent office on 2003-09-11 for new polymer and polymer light-emitting device using the same.
This patent application is currently assigned to SUMITOMO CHEMICAL COMPANY, LIMITED. Invention is credited to Doi, Shuji, Kitano, Makoto, Kobayashi, Satoshi, Nakazono, Akiko, Noguchi, Takanobu, Tsubata, Yoshiaki, Ueoka, Takahiro.
Application Number | 20030168656 10/309101 |
Document ID | / |
Family ID | 19182562 |
Filed Date | 2003-09-11 |
United States Patent
Application |
20030168656 |
Kind Code |
A1 |
Kobayashi, Satoshi ; et
al. |
September 11, 2003 |
New polymer and polymer light-emitting device using the same
Abstract
Provided is a polymer comprising a repeating unit represented by
formula (1), 1 wherein, A.sup.1 represents a divalent group in
which the bond distance ratio (bond distance of
C(.alpha.)-A.sup.1/bond distance of C(.alpha.)-C(.beta.)) is 1.10
or more; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6,
each independently represent a hydrogen atom, alkyl group, alkyloxy
group, aryloxy group, arylalkyloxy group, etc. The polymer is
useful as a light-emitting material, a charge transporting
material, etc.
Inventors: |
Kobayashi, Satoshi;
(Tsukuba-shi, JP) ; Noguchi, Takanobu;
(Tsukuba-shi, JP) ; Tsubata, Yoshiaki;
(Tsukuba-shi, JP) ; Kitano, Makoto; (Tsukuba-shi,
JP) ; Doi, Shuji; (Tsukuba-shi, JP) ; Ueoka,
Takahiro; (Tsukuba-shi, JP) ; Nakazono, Akiko;
(Tsukuba-shi, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 Pennsylvania Avenue, NW
Washington
DC
20037-3213
US
|
Assignee: |
SUMITOMO CHEMICAL COMPANY,
LIMITED
|
Family ID: |
19182562 |
Appl. No.: |
10/309101 |
Filed: |
December 4, 2002 |
Current U.S.
Class: |
257/40 |
Current CPC
Class: |
C09K 2211/1416 20130101;
C08G 2261/1424 20130101; C07F 9/65683 20130101; C08G 2261/3244
20130101; C08G 61/122 20130101; C08G 2261/3243 20130101; C07D
333/76 20130101; Y10T 428/31663 20150401; C07F 7/081 20130101; C09K
11/06 20130101; C08G 2261/5222 20130101; C08G 2261/3162 20130101;
C07D 339/08 20130101 |
Class at
Publication: |
257/40 |
International
Class: |
H01L 035/24 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 7, 2001 |
JP |
2001-373924 |
Claims
What is claimed is:
1. A polymer having a polystyrene reduced number average molecular
weights of 10.sup.3-10.sup.8, and comprising a repeating unit
represented by formula (1), 87wherein, A.sup.1 is a divalent group
represented by -Z- or -Z-Z-, in which Z is an atomic group which
may have a substituent; A.sup.1 represents a divalent group in
which the bond distance ratio (bond distance C2-A.sup.1/bond
distance C2-C1) is 1.10 or more, in which C2 is the carbon of
.alpha. position, and C1 is the carbon of .beta. position,
respectively to A.sup.1; R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, and R.sup.6, each independently represent a hydrogen atom,
a halogen atom, an alkyl group, alkenyl group, alkynyl group,
alkyloxy group, alkylthio group, an alkylamino group, aryl group,
aryloxy group, arylthio group, arylamino group, arylalkyl group,
arylalkyloxy group, aryl alkylthio group, arylalkylamino group,
substituted silyl group, acyl group, acyloxy group, imino group,
amide group, arylalkenyl group, arylalkynyl group, monovalent
heterocyclic group, or cyano group; R.sup.2 and R.sup.3 may be
connected to form a ring; and R.sup.4 and R.sup.5 may be connected
to form a ring.
2. A polymer according to claim 1, wherein the atom in the atomic
group Z includes Si, P, S, Ge, Sn, Se, or Te.
3. A polymer according to claim 1, wherein A.sup.1 is a divalent
group represented by formula (4), (5) or (6), 88wherein, R.sup.7
represents an alkyl group, alkyloxy group, alkylthio group,
alkylamino group, aryl group, aryloxy group, arylthio group,
arylamino group, arylalkyl group, arylalkyloxy group, arylalkylthio
group, arylalkyl amino group, acyl group, acyloxy group, amide
group, or monovalent heterocyclic group, --S--S-- (5) 89wherein,
A.sup.2 represents Si, Ge, or Sn; R.sup.8 and R.sup.9 each
independently represent an alkyl group, alkyloxy group, alkylthio
group, alkylamino group, aryl group, aryloxy group, arylthio group,
arylamino group, arylalkyl group, arylalkyloxy group, arylalkylthio
group, arylalkylamino group, acyloxy group, amide group, or
monovalent heterocyclic group; and l represents 1 or 2.
4. A polymer according to claim 3, wherein A.sup.1 is a divalent
group represented by the above formula (4).
5. A polymer according to claim 3, wherein A.sup.1 is a divalent
group represented by the above formula (5).
6. A polymer according to claim 3, wherein A.sup.1 is a divalent
group represented by the above formula (6), in which A.sup.2 is Si,
and l is 1.
7. A polymer according to claim 3, wherein A.sup.1 is a divalent
group represented by formula (6), in which A.sup.2 is Si, and l is
2.
8. A polymer according to claim 1, wherein R.sup.2 and R.sup.5 each
independently represent an alkyloxy group, alkylthio group,
alkylamino group, aryloxy group, arylthio group, arylamino group,
arylalkyloxy group, arylalkylthio group, or arylalkylamino
group.
9. A polymer according to claim 8, wherein R.sup.2 and R.sup.5 each
independently represent alkyloxy group, aryloxy group, or
arylalkyloxy group.
10. A polymer according to claim 1, wherein said polymer further
comprises a repeating unit represented the below formula (7),
--Ar.sup.6--(CR.sup.17.dbd.CR.sup.18)n- (7) wherein, Ar.sup.6
represents an arylene group or a divalent heterocyclic group;
R.sup.17 and R.sup.18 each independently represent a hydrogen atom,
an alkyl group, aryl group, monovalent heterocyclic group, or cyano
group; and n represents 0 or 1.
11. A polymer according to claim 1, wherein said polymer further
comprises a repeating unit represented by the below formula (8),
90wherein, Ar.sup.1 and Ar.sup.2 each independently represent an
arylene group or a divalent heterocyclic group; R.sup.11 represents
a group represented by an alkyl group, aryl group, monovalent
heterocyclic group, and a group represented by the below formula
(9) or (10); and m represents an integer of 1-4,
--Ar.sup.3Y.sup.1.paren close-st..sub.pR.sup.12 (9) wherein,
Ar.sup.3 represents an arylene group or a divalent heterocyclic
group; R.sup.12 represents a hydrogen atom, an alkyl group, aryl
group, monovalent heterocyclic group, or a group represented by the
below formula (10); Y1 represents --CR.sup.3.dbd.CR.sup.14--, or
--C.ident.C--; R.sup.13 and R.sup.14 each independently represent a
hydrogen atom, an alkyl group, aryl group, monovalent heterocyclic
group, or cyano group; and p represents an integer of 0-2,
91wherein, Ar.sup.4 and Ar.sup.5 each independently represent an
arylene group or a divalent heterocyclic group; R.sup.15 represents
an alkyl group, aryl group, or monovalent heterocyclic group;
R.sup.16 represents a hydrogen atom, an alkyl group, aryl group, or
monovalent heterocyclic group; and q represents an integer of
1-4.
12. A process for producing a polymer according to any one of
claims 1 to 11, wherein condensation polymerization is carried out
using a compound represented by the below formula (11), 92wherein,
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and A.sup.1
respectively represent the same groups as those in formula (1);
x.sup.1 and x.sup.2 each independently represent a substituent
capable of condensation polymerization.
13. A compound represented by formula (11), 93wherein, R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, and A.sup.1
respectively represent the same groups as those in formula (1);
x.sup.1 and x.sup.2 each independently represent a substituent
capable of condensation polymerization.
14. A compound according to claim 13, wherein A.sup.1 is a divalent
group represented by the above formula (4).
15. A compound according to claim 13, wherein A.sup.1 is a divalent
group represented by the above formula (5).
16. A compound according to claim 13, wherein A.sup.1 is a divalent
group represented by the above formula (6), in which A.sup.2 is Si,
and l is 1.
17. A compound according to claim 13, wherein A.sup.1 is a divalent
group represented by the above formula (6), in which A.sup.2 is Si,
and l is 2.
18. A compound according to claim 13, wherein R.sup.2 and R.sup.5
each independently represent an alkyloxy group, alkylthio group,
alkylamino group, aryloxy group, arylthio group, arylamino group,
arylalkyloxy group, arylalkylthio group, or arylalkylamino
group.
19. A compound according to claim 18,wherein R.sup.2 and R.sup.5
each independently represent an alkyloxy group, aryloxy group, or
arylalkyloxy group.
20. A compound according to claim 13, wherein x.sup.1 and x.sup.2
each independently represent a halogen atom, alkyl sulfonate group,
aryl sulfonate group, or arylalkyl sulfonate group.
21. A compound according to claim 13, wherein x.sup.1 and x.sup.2
each independently represent a halogen atom.
22. A process for producing a polymer according to claim 12,
wherein condensation polymerization of the compound recited in
claims 20 or 21 is carried out using a palladium catalyst or a
nickel catalyst.
23. A process for producing a compound according to any one of
claims 14 or 18 to 21, wherein two iodine atoms in the compound
represented by the below formula (13) are selectively metalated,
and then reacted with a dihalogenated phosphorous compound
represented by the below formula (14), 94wherein, R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5 and R.sup.6 respectively represent the
same groups as those in formula (1); x.sup.1 and x.sup.2
respectively represent the same groups as those in formula (11),
95wherein, R.sup.7 represents the same groups as those in formula
(4); x5 and x6 each independently represent a chlorine atom,
bromine atom, or iodine atom.
24. A process for producing a compound according to any one of
claims 15 or 18 to 21, wherein two iodine atoms of the compound
represented by the below formula (13) is selectively metalated, and
then reacted with sulfur.
25. A process for producing a compound according to claim 16,
wherein the compound represented by the below formula (19) is
reacted with a halogenation reagent, 96wherein, R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, R.sup.6 respectively represent the same
groups as those in formula (1); R.sup.8, and R.sup.9 respectively
represent the same groups as those in formula (6).
26. A process for producing a dibenzosilole derivative according to
claim 25, wherein N-halogeno compound is used as the halogenation
reagent.
27. A dibenzosilole derivative represented by the above formula
(19).
28. A dibenzosilole derivative according to claim 27, wherein all
of R.sup.1, R.sup.3, R.sup.4, and R.sup.6 in the above formula (19)
are hydrogen atoms.
29. A process for producing a disilyl compound according to any one
of claims 17 to 21, wherein two iodine atoms in the compound
represented by the above formula (13) are selectively metalated,
and then reacted with a dihalogenated disilyl compound represented
by the below formula (22), 97wherein, R.sup.8 and R.sup.9 represent
respectively represent the same groups as those in formula (6); x11
and x12 each independently represent a chlorine atom, bromine atom,
or iodine atom.
30. A polymer electronic device including a polymer according to
any one of claims 1 to 11.
31. A polymeric fluorescent substance consisting of a polymer
according to any one of claims 1 to 11.
32. A polymer light-emitting device having a light emitting layer
between the electrodes consisting of an anode and a cathode,
wherein said light-emitting layer contains the polymer according to
any one of claims 1 to 11.
33. A flat light source comprising a polymer light-emitting device
according to claim 32.
34. A segment display apparatus comprising a polymer light-emitting
device according to claim 32.
35. A dot-matrix display apparatus comprising a polymer
light-emitting device according to claim 32.
36. A liquid crystal display comprising a polymer light-emitting
device according to claim 32 as a back light.
Description
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a new polymer, a process
for producing the same, a polymeric fluorescent substance thereof,
and a polymer light-emitting device (hereinafter, may be referred
to as "polymer LED") using the same.
[0003] 2. Description of the Related Art
[0004] High molecular weight light-emitting materials and high
molecular weight charge transporting materials are variously
studied since they are soluble in solvents, unlike low molecular
weight materials, and can be formed into light emitting layers or
charge transporting layers by coating method. As the example,
polyfluorene derivatives are known.
SUMMARY OF THE INVENTION
[0005] The object of the present invention is to provide a new
polymer which can be used as a light-emitting material, a charge
transporting material, etc., a process for producing the same, and
a polymer light-emitting device using said polymer.
[0006] That is, the present invention relates to a polymer having a
polystyrene reduced number average molecular weight of
10.sup.3-10.sup.8, and comprising a repeating unit represented by
the below formula (1), 2
[0007] wherein, A.sup.1 is a divalent group represented by -Z- or
-Z-Z- in which Z is an atomic group which may have a substituent;
A.sup.1 represents a divalent group in which the bond distance
ratio (bond distance C2-A.sup.1/bond distance C2-C1) is 1.10 or
more, in which C2 is the carbon of .alpha. position, and C1 is the
carbon of .beta. position, respectively to A.sup.1; R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6, each independently
represent a hydrogen atom, a halogen atom, an alkyl group, alkenyl
group, alkynyl group, alkyloxy group, alkylthio group, an
alkylamino group, aryl group, aryloxy group, arylthio group,
arylamino group, arylalkyl group, arylalkyloxy group, aryl
alkylthio group, arylalkylamino group, substituted silyl group,
acyl group, acyloxy group, imino group, amide group, arylalkenyl
group, arylalkynyl group, monovalent heterocyclic group, or cyano
group; R.sup.2 and R.sup.3 may be connected to form a ring; and
R.sup.4 and R.sup.5 may be connected to form a ring.
DETAILED DESCRIPTION OF THE INVENTION
[0008] In the above formula, as the atom contained in Z, a hetero
atom is preferable, and as the hetero atom, Si, P, S, Ge, Sn, Se
and Te are exemplified.
[0009] Examples of the atomic group Z having substituent are as
follows. 3
[0010] In the formula, R each independently represents a hydrogen
atom, a halogen atom, an alkyl group, alkyloxy group, alkylthio
group, alkylamino group, aryl group, aryloxy group, arylthio group,
arylamino group, arylalkyl group, arylalkyloxy group, arylalkylthio
group, arylalkylamino group, substituted silyl group, acyl group,
acyloxy group, imino group, amide group, arylalkenyl group,
arylalkynyl group, monovalent heterocyclic group, or cyano
group.
[0011] The bond-distance ratio in the above formula (1) is
computable by optimizing the molecular structure of a compound
using quantum-chemistry calculation. As the quantum-chemistry
calculation method, semi-empirical and non-empirical molecular
orbital methods, and a density functional method, etc. can be used.
For example, by a density functional method included in
quantum-chemistry calculation program Gaussian 98, a
structure-optimizing calculation of a compound can be performed
using 6-31 g* as a basis function, and b3lyp as a density
functional approximation, and the bond-distance ratio can be
determined. (Ref: J. Chem. Phys., 98, 5648(1993)).
[0012] The bond distance C2-A.sup.1 is the distance from C2 to the
atom of the group A.sup.1 to which C2 is directly bonded. When the
repeating unit of formula (1) is asymmetrical, both bond distance
ratios are 1.10 or more.
[0013] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and R.sup.6 in
the above formula (1) each independently represent a hydrogen atom,
a halogen atom, an alkyl group, alkenyl group, alkynyl group,
alkyloxy group, alkylthio group, alkylamino group, aryl group,
aryloxy group, arylthio group, arylamino group, arylalkyl group,
arylalkyloxy group, arylalkylthio group, arylalkylamino group,
substituted silyl group, acyl group, acyloxy group, imino group,
amide group, arylalkenyl group, arylalkynyl group, monovalent
heterocyclic group, or cyano group. R.sup.2 and R.sup.3 may be
connected to form a ring; and R.sup.4 and R.sup.5 may be connected
to form a ring.
[0014] Preferably, R.sup.2 and R.sup.5 are each independently
alkyloxy group, alkylthio group, alkylamino group, aryloxy group,
arylthio group, arylamino group, arylalkyloxy group, arylalkylthio
group, or arylalkylamino group among them, and more preferably,
alkyloxy group, aryloxy group, or arylalkyloxy group.
[0015] As the halogen atom, exemplified are fluorine, chlorine,
bromine, and iodine.
[0016] The alkyl group may be any of linear, branched or cyclic,
and usually has about 1 to 20 carbon atoms, and the group may have
a substituent. Specifically, exemplified are: a methyl group, ethyl
group, propyl group, i-propyl group, butyl, i-butyl, t-butyl,
pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl
group, 2-ethyl hexyl group, nonyl group, decyl group,
3,7-dimethyloctyl group, lauryl group, trifluoromethyl group,
pentafluoroethyl group, perfluorobutyl, perfluoro hexyl group,
perfluorooctyl group, etc.; and preferably pentyl group, hexyl
group, octyl group, 2-ethylhexyl group, decyl group, and
3,7-dimethyloctyl group.
[0017] The alkenyl group may be any of linear, branched or cyclic,
and usually has about 2 to 20 carbon atoms, and the group may have
a substituent. Specifically, exemplified are: ethenyl group,
propenyl group, 2-propenyl group, 1-methyl propenyl group,
2-methylpropenyl group, 1,2-dimethyl propenyl group, butenyl group,
2-methylbutenyl group, 1,3-butadienyl group, pentenyl group,
hexenyl group, cyclohexenyl group, heptenyl group, octenyl group,
2-ethyl hexenyl group, trifluoroethenyl group, perfluorobutenyl
group, perfluorohexenyl group, perfluorooctenyl group, etc.
[0018] The alkynyl group may be any of linear, branched or cyclic,
and usually has about 2 to 20 carbon atoms, and the group may have
a substituent. Specifically, exemplified are: ethynyl group,
propynyl group, 2-propynyl group, 2-methyl propynyl group, butynyl
group, 2-methylbutynyl group, 1,3-butanediyl group, pentynyl group,
hexynyl group, cyclohexynyl group, heptynyl group, octynyl group,
2-ethyl hexynyl group, fluoroethynyl group, perfluorobutynyl group,
perfluorohexynyl group, perfluorooctynyl group, etc.
[0019] The alkyloxy group may be any of linear, branched or cyclic,
and usually has about 1 to 20 carbon atoms, and the group may have
a substituent. Specifically, exemplified are: 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, trifluoromethoxy
group, pentafluoroethoxy group, perfluorobutoxy group,
perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group,
2-methoxyethyloxy group, etc.; and preferably pentyloxy group,
hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy
group, and 3,7-dimethyloctyloxy group.
[0020] The alkylthio group may be any of linear, branched or
cyclic, and usually has about 1 to 20 carbon atoms, and the group
may have a substituent. Specifically, exemplified are: methylthio
group, ethylthio group, propylthio group, and i-propylthio group,
butylthio group, i-butylthio group, t-butylthio group, pentylthio
group, hexylthio group, cyclo hexylthio group, heptylthio group,
octylthio group, 2-ethyl hexylthio group, nonylthio group,
decylthio group, 3,7-dimethyloctylthio group, laurylthio group,
trifluoro methylthio group, etc.; and preferaby pentylthio group,
hexylthio group, octylthio group, 2-ethylhexylthio group, decylthio
group, and 3,7-dimethyloctylthio group.
[0021] The alkylthio group may be any of linear, branched or
cyclic, and usually has about 1 to 40 carbon atoms, and the group
may be monoalkylamino group or dialkylamino group. Specifically,
exemplified are: methylamino group, dimethyl amino group,
ethylamino group, diethylamino group, propyl amino group,
dipropylamino group, i-propylamino group, diisopropyl amino group,
butylamino group, i-butylamino group, t-butylamino group,
pentylamino group, hexylamino group, cyclohexylamino group,
heptylamino group, octyl amino group, 2-ethylhexylamino group,
nonylamino group, decylamino group, 3,7-dimethyloctylamino group,
laurylamino group, cyclopentylamino group, dicyclopentylamino
group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl
group, piperidyl group, ditrifluoromethylamino group, etc.; and
preferably pentylamino group, hexylamino group, octyl amino group,
2-ethylhexylamino group, decylamino group, and
3,7-dimethyloctylamino group.
[0022] The aryl group may have a substituent, and usually has about
6 to 60 carbon atoms. Specifically, exemplified are: phenyl group,
C.sub.1-C.sub.12 alkoxyphenyl group (C.sub.1-C.sub.12 shows 1-12
carbon atoms), C.sub.1-C.sub.12 alkylphenyl group, 1-naphthyl
group, 2-naphthyl group, pentafluorophenyl group, etc., and
preferably C.sub.1-C.sub.12 alkoxyphenyl group, and
C.sub.1-C.sub.12 alkylphenyl group.
[0023] The aryloxy group may have a substituent on the aromatic
ring, and usually has about 6 to 60 carbon atoms. Specifically,
exemplified are: phenoxy group, C.sub.1-C.sub.12 alkoxyphenoxy
group, C.sub.1-C.sub.12 alkylphenoxy group, 1-naphtyloxy group,
2-naphtyloxy group, pentafluorophenyloxy group, pyridyloxy group,
pyridazinyloxy group, pyrimidyloxy group, pyrazyloxy group,
triazinyloxy group, etc.; and preferably C.sub.1-C.sub.12
alkoxyphenoxy group, and C.sub.1-C.sub.12 alkyl phenoxy group.
[0024] The arylthio group may have a substituent on the aromatic
ring, and usually has about 6 to 60 carbon atoms. Specifically,
exemplified are: phenylthio group, C.sub.1-C.sub.12
alkoxyphenylthio group, C.sub.1-C.sub.12 alkylphenylthio group,
1-naphthylthio group, 2-naphthylthio group, pentafluoro phenylthio
group, pyridylthio group, pyridazinylthio group, pyrimidylthio
group, pyrazylthio group, triazinylthio group etc.; and preferably
C.sub.1-C.sub.12 alkoxyphenylthio group, and C.sub.1-C.sub.12
alkylphenylthio.
[0025] The arylamino group may have a substituent on the aromatic
ring, and usually has about 6 to 60 carbon atoms. Specifically,
exemplified are: phenylamino group, diphenyl amino group,
C.sub.1-C.sub.12 alkoxyphenylamino group, di(C.sub.1-C.sub.12
alkoxyphenyl)amino group, di(C.sub.1-C.sub.12 alkylphenyl)amino
group, 1-naphtylamino group, 2-naphtylamino group,
pentafluorophenylamino group, pyridylamino group, pyridazinylamino
group, pyrimidylamino group, pyrazylamino group, triazinylamino
group etc.; and preferably C.sub.1-C.sub.12 alkylphenylamino group,
and di(C.sub.1-C.sub.12 alkylphenyl)amino group.
[0026] The arylalkyl group may have a substituent, and usually has
about 7 to 60 carbon atoms. Specifically, exemplified are:
phenyl-C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12
alkoxyphenyl-C.sub.1-C.sub.12 alkyl group, C.sub.1-C.sub.12
alkylphenyl-C.sub.1-C.sub.12 alkyl group,
1-naphtyl-C.sub.1-C.sub.12 alkyl group, 2-naphtyl-C.sub.1-C.sub.12
alkyl group, etc., and preferably C.sub.1-C.sub.12
alkoxyphenyl-C.sub.1-C.sub.12 alkyl group, and C.sub.1-C.sub.12
alkylphenyl-C.sub.1-C.sub.12 alkyl group.
[0027] The arylalkyloxy group may have a substituent, and usually
has about 7 to 60 carbon atoms. Specifically, exemplified are:
phenyl-C.sub.1-C.sub.12 alkyloxy group, C.sub.1-C.sub.12 alkyloxy
phenyl-C.sub.1-C.sub.12 alkyloxy group, C.sub.1-C.sub.12
alkylphenyl-C.sub.1-C.sub.12 alkyloxy group,
1-naphtyl-C.sub.1-C.sub.12 alkyloxy group,
2-naphtyl-C.sub.1-C.sub.12 alkyloxy group, etc.; and preferably
C.sub.1-C.sub.12 alkyloxy phenyl-C.sub.1-C.sub.12 alkyloxy group,
and C.sub.1-C.sub.12 alkylphenyl-C.sub.1-C.sub.12 alkyloxy
group.
[0028] The arylalkylthio group may have a substituent, and usually
has about 7 to 60 carbon atoms. Specifically, exemplified are:
phenyl-C.sub.1-C.sub.12 alkylthio group, C.sub.1-C.sub.12 alkyloxy
phenyl-C.sub.1-C.sub.12 alkylthio group, C.sub.1-C.sub.12
alkylphenyl-C.sub.1-C.sub.12 alkylthio group,
1-naphtyl-C.sub.1-C.sub.12 alkylthio group,
2-naphtyl-C.sub.1-C.sub.12 alkylthio group, etc.; and preferably
C.sub.1-C.sub.12 alkyloxy phenyl-C.sub.1-C.sub.12 alkylthio group,
and C.sub.1-C.sub.12 alkylphenyl-C.sub.1-C.sub.12 alkylthio
group.
[0029] The arylalkylamino group usually has about 7 to 60 carbon
atoms. Specifically, exemplified are: phenyl-C.sub.1-C.sub.12 alkyl
amino group, C.sub.1-C.sub.12 alkoxyphenyl-C.sub.1-C.sub.12
alkylamino group, C.sub.1-C.sub.12 alkylphenyl-C.sub.1-C.sub.12
alkylamino group, di(C.sub.1-C.sub.12 alkoxy
phenyl-C.sub.1-C.sub.12 alkyl)amino group, di(C.sub.1-C.sub.12
alkylphenyl-C.sub.1-C.sub.12 alkyl)amino group,
1-naphtyl-C.sub.1-C.sub.12 alkylamino group,
2-naphtyl-C.sub.1-C.sub.12 alkylamino group, etc.; and preferably
C.sub.1-C.sub.12 alkylphenyl-C.sub.1-C.sub.12 alkylamino group, and
di(C.sub.1-C.sub.12 alkylphenyl-C.sub.1-C.sub.12 alkyl)amino
group.
[0030] As the substituted silyl group, specifically exemplified
are: trialkylsilyl groups, such as trimethylsilyl group,
triethylsilyl group, tripropylsilyl group, tri-1-propylsilyl group,
dimethyl-1-propylsilyl group, diethyl-1-propylsilyl group,
t-butyldimethylsilyl group, pentyldimethylsilyl group,
hexyldimethylsilyl group, heptyldimethyl silyl group,
octyldimethylsilyl group, 2-ethylhexyldimethylsilyl group,
nonyldimethylsilyl group, decyldimethylsilyl group,
3,7-dimethyloctyl-dimethylsilyl group, and lauryldimethylsilyl
group, and the like; triarylsilyl groups, such as triphenyl silyl
group, tri-p-xylylsilyl group, and the like; tri(arylalkyl)silyl
groups, such as tribenzylsilyl group, and the like;
(alkyl)(aryl)silyl groups, such as diphenylmethylsilyl group,
t-butyl diphenylsilyl group, dimethylphenylsilyl group, and the
like; mono(arylalkyl)silyl groups, such as phenyl-C.sub.1-C.sub.12
alkylsilyl group, C.sub.1-C.sub.12 alkyloxyphenyl-C.sub.1-C.sub.12
alkylsilyl group, C.sub.1-C.sub.12 alkylphenyl-C.sub.1-C.sub.12
alkylsilyl group, 1-naphtyl-C.sub.1-C.sub.12 alkylsilyl group,
2-naphtyl-C.sub.1-C.sub.12 alkylsilyl group, and the like; and
mono(arylalkyl)dialkylsilyl groups, such as phenyl-C.sub.1-C.sub.12
alkyldimethyl silyl group, and the like.
[0031] Pentyldimethylsilyl group, hexyldimethylsilyl group,
octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group,
decyldimethylsilyl group, 3,7-dimethyloctyldimethylsilyl group,
C.sub.1-C.sub.12 alkyloxyphenyl-C.sub.1-C.sub.12 alkylsilyl group,
C.sub.1-C.sub.12 alkylphenyl-C.sub.1-C.sub.12 alkylsilyl group are
preferable.
[0032] The acyl group has usually 2 to 20 carbon atoms, and
specifically exemplified are acetyl group, propionyl group, butyryl
group, isobutyryl group, pivaloyl group, benzoyl group,
trifluoroacetyl group, pentafluorobenzoyl group, etc.
[0033] The acyloxy group usually has 2 to 20 carbon atoms, and
specifically exemplified are acetyloxy group, propionyloxy group,
butyryloxy group, isobutyryloxy group, pivaloyloxy group,
benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyloxy
group, etc.
[0034] The imino group usually has about 2 to 20 carbon atoms.
Specifically, groups represented by following structural formulas
etc. are exemplified. 4
[0035] The amide group usually has 2 to 20 carbon atoms, and
specifically exemplified are formamide group, acetamide group,
propioamide group, butyroamide group, benzamide group,
trifluoroacetamide group, pentafluorobenzamide group, diformamide
group, diacetoamide group, dipropioamide group, dibutyroamide
group, dibenzamide group, ditrifluoro acetamide group,
dipentafluorobenzamide group, succinimide group, phthalic-imide
group, etc.
[0036] The arylalkenyl group usually has 7 to 60 carbon atoms, and
specifically exemplified are phenyl-C.sub.2-C.sub.12 alkenyl group,
C.sub.1-C.sub.12 alkyloxyphenyl-C.sub.2-C.sub.12 alkenyl group,
C.sub.1-C.sub.12 alkyl phenyl-C.sub.2-C.sub.12 alkenyl group,
1-naphtyl-C.sub.2-C.sub.12 alkenyl group,
2-naphtyl-C.sub.2-C.sub.12 alkenyl group, etc.; and preferably
C.sub.1-C.sub.12 alkyloxy phenyl-C.sub.2-C.sub.12 alkenyl group,
and C.sub.1-C.sub.12 alkyl phenyl-C.sub.2-C.sub.12 alkenyl
group.
[0037] The arylalkynyl group usually has 7 to 60 carbon atoms, and
specifically exemplified are phenyl-C.sub.2-C.sub.12 alkynyl group,
C.sub.1-C.sub.12 alkyloxyphenyl-C.sub.2-C.sub.12 alkynyl group,
C.sub.1-C.sub.12 alkyl phenyl-C.sub.2-C.sub.12 alkynyl group,
1-naphtyl-C.sub.2-C.sub.12 alkynyl group,
2-naphtyl-C.sub.2-C.sub.12 alkynyl group, etc.; and preferably
C.sub.1-C.sub.12 alkyloxyphenyl-C.sub.2-C.sub.12 alkynyl group, and
C.sub.1-C.sub.12 alkylphenyl-C.sub.2-C.sub.12 alkynyl group.
[0038] The monovalent heterocyclic group means an atomic group in
which a hydrogen atom is removed from a heterocyclic compound, and
usually has about 4 to 60 carbon atoms. Specifically, exemplified
are: thienyl group, C.sub.1-C.sub.12 alkyl thienyl group pyroryl
group, furyl group, pyridyl group, C.sub.1-C.sub.12 alkylpyridyl
group, etc.; and preferably thienyl group, C.sub.1-C.sub.12
alkylthienyl group, pyridyl group, and C.sub.1-C.sub.12
alkylpyridyl group.
[0039] Among them, A.sup.1 in the above formula (1) is preferably a
divalent group represented by the below formula (4), (5), or (6).
5
[0040] [in the formula, R.sup.7 represents an alkyl group, alkyloxy
group, alkylthio group, alkylamino group, aryl group, aryloxy
group, arylthio group, arylamino group, arylalkyl group,
arylalkyloxy group, arylalkylthio group, arylalkylamino group, acyl
group, acyloxy group, amide group, or monovalent heterocyclic
group.]
--S--S-- (5) 6
[0041] [in the formula, A.sup.2 represents Si, Ge, or Sn. R.sup.8
and R.sup.9 each independently represent alkyl group, alkyloxy
group, alkylthio group, alkylamino group, aryl group, aryloxy
group, arylthio group, arylamino group, arylalkyl group,
arylalkyloxy group, arylalkylthio group, arylalkylamino group,
acyloxy group, amide group, or monovalent heterocyclic group. l
represents 1 or 2.]
[0042] Among them, in the above formula (1), preferables are: a
polymer whose A.sup.1 is a divalent group represented by the above
formula (4); a polymer whose A.sup.1 is a divalent group
represented by the above formula (5); a polymer whose A.sup.1 is a
divalent group represented by formula (6), A.sup.2 is Si, and l is
1; and a polymer whose A.sup.1 is a divalent group represented by
formula (6), A.sup.2 is Si, and l is 2.
[0043] Specific examples of the divalent group whose A.sup.1 is
represented by the above formula (4) include followings.
7891011121314
[0044] Specific examples of the divalent group whose A.sup.1 is
represented by the above formula (5) include followings.
1516171819
[0045] Specific examples of the divalent group whose A.sup.1 is
represented by the above formula (6), A.sup.2 is Si, and l is 1
include followings. 202122232425262728
[0046] Specific examples of the divalent group whose A.sup.1 is
represented by the above formula (6), A.sup.2 is Si, and l is 2
include followings. 29303132333435
[0047] In the above formula, Me represents a methyl group, Ph
represents a phenyl group, Bn represents a benzyl, and Ac
represents an acetyl group.
[0048] The polymer of the present invention may contain two or more
kinds of repeating units represented by the above formula (1).
[0049] The amount of the repeating unit shown by the above formula
(1) is usually 1 to 100% by mole based on the sum of total moles of
all repeating units contained in the polymer of the present
invention, preferably 40 to 90% by mole, and more preferably 70 to
85% by mole.
[0050] The polymer of the present invention may contain a repeating
unit other than the repeating unit represented by the above formula
(1). As the repeating unit other than formula (1), exemplified are
a repeating unit represented by the below formula (7), and a
repeating unit represented by formula (8)after-mentioned.
--Ar.sup.6--(CR.sup.17.dbd.CR.sup.18)n- (7)
[0051] [in the formula, Ar.sup.6 represents an arylene group or a
divalent heterocyclic group, R.sup.17 and R.sup.18 each
independently represent a hydrogen atom, an alkyl group, aryl
group, monovalent heterocyclic group, or cyano group; and n
represents 0 or 1.]
[0052] In view of the life time of a device, the repeating unit
represented by the after-mentioned formula (8) is preferable.
[0053] The Ar.sup.6 may have a substituent, such as an alkyl group,
alkyloxy group, alkylthio group, alkylamino group, aryl group,
aryloxy group, arylthio group, arylamino group, arylalkyl group,
arylalkyloxy group, arylalkylthio group, arylalkylamino group,
substituted silyl group, acyl group, acyloxy group, imino group,
amide group, imide group, arylalkenyl group, arylalkynyl group,
monovalent heterocyclic group, or cyano group. Specific examples of
these substituents represent the same as aforementioned. When
Ar.sup.6 has a plurality of substituents, they may be mutually the
same or different.
[0054] The arylene group in the present invention includes those
containing a benzene ring, a condensed ring, and two or more of
independent benzene rings or condensed rings bonded through a group
such as a direct bond, a vinylene group or the like. The arylene
group has usually 6 to 60 carbon atoms, preferably 6 to 20 carbon
atoms. As the arylene group, exemplified are phenylene group (for
example, following formula (26)), naphthalenediyl group (following
formula (27)), anthracenylene group (following formula (28)),
biphenylene group (following formula (29)), triphenylene group
(following formula (30)), condensed ring compound group (following
formula (31)), etc. 363738
[0055] In the present invention, the divalent heterocyclic group is
an atomic group in which two hydrogen atoms are removed from a
heterocyclic compound, and usually has 4 to 60 carbon atoms,
preferably 4 to 20 carbon atoms. They may have a substituent on the
hetero-ring and the carbon atoms of the substituent are not counted
as the carbon atoms of the heterocyclic group.
[0056] 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.
[0057] As the divalent heterocyclic compound group, followings are
exemplified.
[0058] Divalent heterocyclic compound group containing a nitrogen
as a hetero atom; pyridine-diyl group (following formula (32)),
diaza phenylene group (following formula (33)), quinolinediyl group
(following formula (34)), quinoxaline diyl group (following formula
(35)), acridine diyl group (following formula (36)), bipyridyl diyl
group (following formula (37)), phenanthroline diyl group
(following formula (38)), etc.; groups containing a hetero atom,
such as silicon, nitrogen, sulfur, selenium, etc. and having a
fluorene structure (following formula (39));
[0059] 5 membered-ring heterocyclic compound group containing a
hetero atom such as silicon, nitrogen, sulfur, selenium, etc.
(following formula (40));
[0060] 5 membered-ring condensation heterocyclic compound group
containing a hetero atom such as silicon, nitrogen, sulfur,
selenium, etc. (following formula (41)), benzothiadiazole-4,7-diyl
group, benzo-oxadiazole-4,7-diyl group, etc.;
[0061] group in which 5 membered ring heterocyclic compound group
containing silicon, nitrogen, sulfur, selenium, etc. as a hetero
atom is connected with a phenyl group at the a position of the
hetero atom to form a dimer or oligomer (following formula (42));
and
[0062] group in which 5 membered ring heterocyclic compound group
containing silicon, nitrogen, sulfur, selenium, etc. as a hetero
atom is connected with a phenyl group at the a position of the
hetero atom (following formula (43)). 3940414243
[0063] In the above formula, R' each independently represents a
hydrogen atom, a halogen atom, an alkyl group, alkyloxy group,
alkylthio group, alkyl amino group, aryl group, aryloxy group,
arylthio group, aryl amino group, arylalkyl group, arylalkyloxy
group, aryl alkylthio group, arylalkylamino group, acyloxy group,
amide group, arylalkenyl group, arylalkynyl group, monovalent
heterocyclic group, or cyano group. R" represents a hydrogen atom,
an alkyl group, aryl group, arylalkyl group, silyl group, acyl
group, or monovalent heterocyclic group.
[0064] The divalent heterocyclic group includes, for example, a
triplet luminescence complex etc. and the following divalent
metal-complex groups are exemplified. 4445
[0065] As the examples of the arylene group or divalent
heterocyclic group, the arylene groups or divalent heterocyclic
groups contained in the materials conventionally used as EL
luminescence materials are also exemplified. These materials are
disclosed in, for example, WO 99/12989, WO 00/55927, WO 01/49769A1,
WO01/49768A2, WO98/06773, U.S. Pat. No. 5,777,070, WO 99/54385, WO
00/46321, and U.S. Pat. No. 6,169,163B1.
[0066] The repeating unit other than the repeating unit represented
by the above formula (1), preferably contains a repeating unit
represented by the below formula (8), in view of life time of a
device. 46
[0067] [in the formula, Ar.sup.1 and Ar.sup.2 each independently
represent an arylene group or divalent heterocyclic group; R.sup.11
represents an alkyl group, aryl group, monovalent heterocyclic
group, a group represented by the below formula (9) or (10); m
represents an integer of 1 to 4,
--Ar.sup.3Y.sup.1.paren close-st..sub.pR.sup.12 (9)
[0068] (in the formula, Ar.sup.3 represents an arylene group or
divalent heterocyclic group; R.sup.12 represents a hydrogen atom,
an alkyl group, aryl group, monovalent heterocyclic group, or a
group represented by the below formula (10); Y.sup.1 represents
[0069] --CR.sup.13.dbd.CR.sup.14--, or --C.ident.C--; R.sup.13 and
R.sup.14 each independently represent a hydrogen atom, an alkyl
group, aryl group, monovalent heterocyclic group, or cyano group; p
represents an integer of 0-2), 47
[0070] (in the formula, Ar.sup.4 and Ar.sup.5 each independently
represent an arylene group or a divalent heterocyclic group;
R.sup.15 represents an alkyl group, aryl group, or monovalent
heterocyclic group; R.sup.16 represents a hydrogen atom, an alkyl
group, aryl group, or monovalent heterocyclic group; q represents
an integer of 1 to 4)].
[0071] Specific examples of the arylene group, and divalent
heterocyclic group for Ar.sup.1-Ar.sup.5 in the above formulas
(8)-(10) are the same as those aforementioned. Specific examples of
the alkyl group, aryl group, and monovalent heterocyclic group for
R.sup.11-R.sup.16 in the above formulas (8)-(10) are the same as
those aforementioned.
[0072] As the preferable examples of the repeating unit represented
by the above formula (8), exemplified are the followings which may
have a substituent on the benzene ring or heterocyclic ring. As the
substituent, a halogen atom, an alkyl group, alkyloxy group,
alkylthio group, alkylamino group, aryl group, aryloxy group,
arylthio group, arylamino group, arylalkyl group, arylalkyloxy
group, arylalkylthio group, arylalkylamino group, acyl group,
acyloxy group, amide group, imino group, silyl group, silyloxy
group, silylthio group, silylamino group, monovalent heterocyclic
group, arylalkenyl group, arylethynyl group, and cyano group are
exemplified. 48495051
[0073] The repeating units contained in the polymer of the present
invention may be connected by non-conjugated units, and may have a
non-conjugated portion in the repeating units themselves.
[0074] As the non-conjugated unit, exemplifeid are groups shown
below, those in which the group shown below is combined with a
vinylene groups, and those in which two of more kinds of the groups
shown below are combined. R is a group selected from the group
consisting of a hydrogen atom, alkyl group having 1 to 20 carbon
atoms, aryl group having 6 to 60 carbon atoms, and a heterocyclic
group having 4 to 60 carbon atoms, and Ar represents a hydrocarbon
group having 6 to 60 carbon atoms. 52
[0075] The polymer may also be a random, block or graft copolymer,
or a polymer having an intermediate structure thereof, for example,
a random copolymer having block property. From the viewpoint for
obtaining a polymer having high fluorescent quantum yield, random
copolymers having block property and block or graft copolymers are
more preferable than complete random copolymers. Further, the
polymer have a branched main chain and more than three terminals,
and a dendrimer.
[0076] The end group of polymer may also be protected with a stable
group since if a polymerization active group remains intact, there
is a possibility of reduction in light emitting property and
life-time when the fluorescent substance is made into an device.
Those having a conjugated bond continuing to a conjugated structure
of the main chain are preferable, and there are exemplified
structures connected to an aryl group or heterocyclic compound
group via a carbon-carbon bond. Specifically, substituents of the
chemical formula 10 in JP-A No. 9-45478 are exemplified.
[0077] The polymer has a polystyrene reduced number average
molecular weight of 10.sup.3 to 10.sup.8. Degree of polymerization
thereof changes according to the structure of the repeating units
or the ratio thereof. From the viewpoint of film-molding property,
generally the total number of repeating units are preferably 20 to
10000, more preferably 30 to 10000, and further preferably 50 to
5000.
[0078] As good solvents for the polymer, there are exemplified
chloroform, methylene chloride, dichloroethane, tetrahydrofuran,
toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and
the like. The polymer can be usually dissolved in these solvents in
an amount of 0.1 wt % or more, though the amount differs depending
on the structure and molecular weight of the polymer.
[0079] The polymer of the present invention can be manufactured by
condensation polymerization, using a compound represented by the
below formula (11). 53
[0080] (in the formula, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, and A.sup.1 represent the same as those in
formula (1); x.sup.1 and x.sup.2 each independently represent a
substituent capable of condensation polymerization.)
[0081] As the substituents capable of condensation polymerization,
exemplified are: a halogen atom, alkyl sulfonate group, aryl
sulfonate group, arylalkyl sulfonate group, borate group, sulfonium
methyl group, phosphonium methyl group, phosphonate methyl group,
monohalogenated-methyl group, boric-acid group, formyl group, cyano
group, vinyl group, etc.; and preferably a halogen atom, alkyl
sulfonate group, aryl sulfonate group, and arylalkyl sulfonate
group.
[0082] Here, as the alkyl sulfonate group, methane sulfonate group,
ethane sulfonate group, trifluoromethane sulfonate group, etc. are
exemplified. As the aryl sulfonate group, benzene sulfonate group,
p-toluene sulfonate group, etc. are exemplified. As the aryl
sulfonate group, benzyl sulfonate group etc. are exemplified.
[0083] As the boric-acid ester group, groups represented by the
below formulas are exemplified. 54
[0084] In the formula, Me shows a methyl group and Et shows an
ethyl group.
[0085] As the sulfonium methyl group, groups represented by the
below formulas are exemplified.
--CH.sub.2S.sup.+Me.sub.2X.sup.-, --CH.sub.2S.sup.+Ph.sub.2X
[0086] (X shows a halogen atom and Ph shows a phenyl group.)
[0087] As the phosphonium methyl group, groups represented by the
below formulas are exemplified.
--CH.sub.2P.sup.+Ph.sub.3X.sup.- (X shows a halogen atom)
[0088] As the phosphonate methyl group, groups represented by the
below formulas are exemplified.
--CH.sub.2PO(OR').sub.2 (R' shows an alkyl group, an aryl group, or
an arylalkyl group.)
[0089] As the monohalogenated-methyl group, fluoromethyl group,
chloromethyl group, bromomethyl group, and iodomethyl group are
exemplified.
[0090] For example, in the above formula (1), a polymer whose
A.sup.1 is a divalent group represented by the above formula (4)
can be manufactured by using a compound whose A.sup.1 is a divalent
group represented by the above formula (4) in the above formula
(11).
[0091] Moreover, a polymer whose A.sup.1 is a divalent group
represented by the above (5) formula in the above formula (1) can
be manufactured, by using a compound whose A.sup.1 is a divalent
group represented by the above (5) formula in the above formula
(11).
[0092] A polymer whose A.sup.1 is a divalent group represented by
the above (6) formula in the above formula (1), A.sup.2 is Si, and
l is 1, can be manufactured by using a compound whose A.sup.1 is a
divalent group represented by the above (6) formula in the above
formula (11), and A.sup.2 is Si, and l is 1 is used.
[0093] Furthermore, a polymer whose A.sup.1 is a divalent group,
represented by the above (6) formula in the above formula (1),
A.sup.2 is Si, and l is 2, can be manufactured by using a compound
whose A.sup.1 is a divalent group represented by the above (6)
formula in the above formula (11), and A.sup.2 is Si, and l is 2 is
used.
[0094] Moreover, when the polymer of the present invention has a
repeating unit other than the repeating unit of formula (1), a
condensation polymerization just can be carried out using together
with a monomer as the repeating unit other than the repeating unit
of formula (1).
[0095] As the monomer used as the repeating unit other than the
repeating unit of formula (1), compounds of the below formulas
(7-2) and (8-2) are exemplified, and the below formula (8-2) is
preferable.
X.sup.1--Ar.sup.6--(CR.sup.17.dbd.CR.sup.18).sub.n--X.sup.2
(7-2)
[0096] (In the formula, Ar.sup.6, R.sup.17 and R.sup.18 represent
the same as those in formula (7); x.sup.1 and x.sup.2 are the same
as those in formula (11); n represents an integer of 0-1.) 55
[0097] (In the formula, Ar.sup.1, Ar.sup.2, and R.sup.11 represent
the same as those in formula (8); x.sup.1 and x.sup.2 represent the
same as those in formula (11); m represents an integer of 0-4.)
[0098] In the manufacture method of the polymer of the present
invention, as the method of carrying out condensation
polymerization of a compound represented by the above formula (11)
which is a raw material, and a monomer as the repeating unit other
than the repeating unit of formula (1), known condensation
reactions can be used according to the kind of substituents used
for condensation polymerization in each of monomers according to
requirements.
[0099] As a method of producing the polymer of the present
invention, for example, a method described in JP-A No. 5-202355 is
exemplified, when a vinylene group is contained in the main chain.
Namely, there are exemplified methods such as polymerization of a
compound having a formyl group with a compound having a phosphonium
methyl group, or of a compound having a formyl group and a
phosphonium methyl group, according to a Wittig reaction,
polymerization of a compound having a vinyl group with a compound
having a halogen atom, according to a Heck reaction,
polycondensation of a compound having two or more halogenated
methyl groups, according to a de-hydrohalogenating method,
polycondensation of a compound having two or more sulfonium salt
groups, according to a sulfonium salt-decomposing method,
polymerization of a compound having a formyl group with a compound
having a cyano group, according to a Knoevenagel reaction,
polymerization of a compound having two or more formyl groups,
according to McMurry reaction, and the like.
[0100] When a vinylene group is not contained in the main chain,
for example, a method of polymerization from corresponding monomers
by a Suzuki coupling reaction, a method of polymerization by a
Grignard reaction, a method of polymerization using a Ni(O)
catalyst, a method of polymerization using an oxidizer such as
FeCl.sub.3 and the like, a method of oxidation polymerization
electrochemically, a method of decomposition of an intermediate
polymer having a suitable releasing group, and the like are
exemplified.
[0101] Of these, the polymerization method by a Wittig reaction,
the polymerization method by a Heck reaction, the polymerization
method by a Horner-Wadsworth-Emmons method, the polymerization
method by a Knoevenagel reaction, the polymerization method by a
Suzuki coupling reaction, the polymerization method by a Grignard
reaction and the polymerization method using a Ni(O) catalyst are
preferable since structure control is easy in these methods.
[0102] Among the manufacture methods of the present invention, it
is suitable to conduct a condensation polymerization of a compound
as a monomer represented by the above formula (11) in which x.sup.1
and x.sup.2 are each independently a halogen atom, alkyl sulfonate
group, aryl sulfonate group or arylalkyl sulfonate group,
preferably a halogen atom, using a palladium catalyst or a nickel
catalyst.
[0103] In the manufacture method of the present invention, the
compound of the above formula (11) used as a raw material monomer,
and a monomer, such as the above formula (7-2) or a formula (8-2)
are, if necessary, dissolved in an organic solvent, and reacted at
a temperature of below the boiling point and above the melting
point of the organic solvent, using an alkali or a suitable
catalyst, if necessary. For example, known methods can be used,
described in "Organic Reactions", vol. 14, pp. 270 to 490, John
Wiley & Sons, Inc., 1965, "Organic Reactions", vol. 27, pp. 345
to 390, John Wiley & Sons, Inc., 1982, "Organic Synthesis",
Collective Volume VI, pp. 407 to 411, John Wiley & Sons, Inc.,
1988, Chemical Review, vol. 95, p. 2457 (1995), Journal of
Organometallic Chemistry, vol. 576, p. 147 (1999), Journal of
Praktical Chemistry, vol. 336, p. 247 (1994), Makromolecular
Chemistry Macromolecular Symposium, vol. 12, p. 229 (1987), and the
like.
[0104] It is preferable that the organic solvent used is subjected
to a deoxygenation treatment sufficiently and the reaction is
progressed under an inert atmosphere, generally for suppressing a
side reaction, though the treatment differs depending on compounds
and reactions used. Further, it is preferable to conduct a
dehydration treatment likewise (however, this is not applicable in
the case of a reaction in a two-phase system with water, such as a
Suzuki coupling reaction).
[0105] In order to promote the reaction, an alkali or a catalyst is
added appropriately. These may be selected according to the
reaction. It is preferable that the alkali or catalyst is soluble
sufficiently in a solvent used for the reaction. As the method of
mixing an alkali or catalyst, there is exemplified a method of
adding a solution of an alkali or catalyst slowly while stirring
under an inner atmosphere of argon and nitrogen and the like or a
method of slowly adding the reaction solution to a solution of an
alkali or catalyst, inversely.
[0106] It is preferable to polymerize, after purifying the monomer
before a polymerization by methods, such as distillation,
sublimation purification, and recrystallization, since the purity
may affect the performance of devices, such as luminescence
characteristics, when using the polymer of the present invention
for polymer LED. Moreover, it is preferable to carry out
purification processing such as reprecipitation purification, and
fractionation by chromatography etc. after polymerization.
[0107] A compound represented by the below formula (12) which is a
divalent group whose A.sup.1 in the above formula (11) is
represented by the above (4) formula, 56
[0108] can be prepared by: after metalating the two iodine atoms of
the compound below formula (13) selectively, 57
[0109] [in the formula, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, x.sup.1 and x.sup.2 represent the same as the
above], and reacting it with a dihalogenated phosphorous compound
represented by the below formula (14), 58
[0110] [in the formula, R.sup.7 represents the same as the above;
x5 and x6 each independently represents a chlorine atom, a bromine
atom, or an iodine atom.]
[0111] The reaction can be carried out under inert atmospheres,
such as nitrogen and argon, in the presence of a solvent. As the
solvent used for reaction, exemplified are: saturated hydrocarbons,
such as pentane, hexane, heptane, octane, and cyclohexane;
unsaturated hydrocarbons, such as benzene, toluene, xylene, and
ethylbenzene; ethers, such as dimethyl ether, diethyl ether,
methyl-t-butyl ether, di-t-butyl ether, tetrahydrofuran,
tetrahydropyran, and dioxane; and amines, such as trimethylamine,
triethylamine, N,N,N',N'-tetramethylethylenediamine, and pyridine.
These may be used as alone or a mixture thereof.
[0112] As the metalating agent, methyl lithium, n-butyl lithium,
sec-butyl lithium, t-butyl lithium, phenyl lithium, etc. are
exemplified. The reaction temperature is usually -30.degree. C. or
less, and preferably -80.degree. C. or less in order to metalate
selectively.
[0113] Moreover, it may be reacted with the dihalogenated
phosphorous compound represented by the above formula (14) after
exchanging the metal of the compound metalated by the above
method.
[0114] As the metal exchanging reagent, magnesium salts, such as
magnesium chloride and a magnesium bromide; copper salt, such as
copper chloride (I), copper chloride (II), copper bromide (I),
copper bromide (II), and copper iodide (I); and zinc salts, such as
zinc chloride, and zinc bromide, and zinc iodide, are exemplified.
In view of yield, magnesium salt is preferable.
[0115] As for the reaction with a dihalogenated phosphorous
compound represented by the above formula (14), it is preferable to
carry out at from -100.degree. C. to the boiling point of a
solvent.
[0116] After the reaction, it can be obtained by a usual
post-treatment, for example, quenching with water, then extracting
by an organic solvent, and distilling of the solvent. When the
product is unstable to water, it can be obtained by a method of
distilling a solvent after removing inorganic salt by
filtration.
[0117] Isolation and purification of the product can be performed
by a method, such as recrystallization, distillation, or
fractionation by chromatography.
[0118] Moreover, a compound represented the below formula (15)
whose A.sup.1 is a divalent group represented by the above formula
(5) in the above formula (11), 59
[0119] can be manufactured by: after metalating the two iodine
atoms of the compound represented by the above formula (13), and
reacting it with sulfur.
[0120] About the reaction method, it is the same as that of the
synthetic process of the compound represented by the above formula
(12). About the reaction with sulfur, it may be added as any form
of solid, or dissolved or suspended in a solvent. The temperature
of the reaction is from -100.degree. C. to 30.degree. C., and
preferably from -80.degree. C. to 0.degree. C. About the
post-treatment of reaction, and the purification method, it is also
the same as that of the compound represented by the above formula
(12).
[0121] A compound represented by the below formula (20) whose
A.sup.1 is a divalent group represented by the above formula (6) in
the above formula (11), and A.sup.2 is Si, and l is 2, 60
[0122] can be manufactured by: after metalating the two iodine
atoms of the compound represented by the above formula (13), and
reacting it with 1,2-dihalogenated disilyl compound represented by
the below formula (22), 61
[0123] [in the formula, R.sup.8 and R.sup.9 represent the same as
the above. x11 and x12 each independently represent a chlorine
atom, a bromine atom, or an iodine atom.]
[0124] About the reaction method, post-treatment, and purification
method, it is the same as those of the compound represented by the
above formula (12).
[0125] Moreover, similarly with the compound represented by the
above formula (12), the compound represented by the below formula
(3-2) can be manufactured by reacting it with the dihalogenated
compound after metalating the two iodine atoms of the compound
represented by the above formula (13) selectively. About the method
of reaction, post-treatment, and purification method, it is the
same as those of the compound represented by the above formula
(12). 62
[0126] (In the formula, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, and R.sup.6 represent the same as those in formula (11).
x.sup.1 and x.sup.2 are represent the same as those in formula
(11). A.sup.3 represents a divalent group selected from 63
[0127] In the formula, R represents the same as aforementioned.)
About the reaction method, post-treatment, and purification method,
it is the same as those of the compound represented by the above
formula (12).
[0128] A dibenzosilole derivative represented by the below formula
(18) whose A.sup.1 is a divalent group represented by the above
formula (6) in the above formula (11), and A.sup.2 is Si, and l is
1, 64
[0129] can be manufactured by reacting a compound (dibenzosilole
derivative) represented by the below formula (19), with a
halogenation reagent, preferably an N-halogeno compound, 65
[0130] (in the formula, R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, R.sup.6, R.sup.8, and R.sup.9 represent the same as those
in formula (11).)
[0131] The reaction can be carried out under inert atmosphere such
as nitrogen and argon, in the presence of a solvent. The reaction
temperature is preferably from -80.degree. C. to the boiling point
of the solvent.
[0132] Moreover, it can be manufactured also by a method in which a
halogenation reagent is reacted, after reacting the compound
represented by formula (19) with a base.
[0133] As the N-halogeno compound, N-chloro succinimide, N-chloro
phthalic imide, N-chloro diethylamine, N-chloro dibutyl amine,
N-chloro cyclohexyl amine, N-bromosuccinimide, N-bromo
phthalic-imide, N-bromo ditrifluoromonomethylamine, N-iodo
succinimide, N-iodophthalic imide, etc. are exemplified. As the
other halogenation reagents, fluorine, fluoroxy trifluoromethane,
oxygen difluoride, perchloryl fluoride, cobalt fluoride (III),
silver fluoride (II), selenium fluoride (IV), manganese fluoride
(III), chlorine, iodine trichloride, aluminum trichloride,
tellurium chloride (IV), molybdenum chloride, antimony chloride,
iron chloride (III), titanium tetrachloride, phosphorus
pentachloride, thionyl chloride, bromine, 1,2-dibromo ethane, boron
tribromide, copper bromide, silver bromide, t-butyl bromide,
bromine oxide, iodine, iodine monochloride, etc. are
ecemplified.
[0134] As the solvent used for reaction, exemplified are: saturated
hydrocarbons, such as pentane, hexane, heptane, octane,
cyclohexane; unsaturated hydrocarbons, such as benzene, toluene,
ethylbenzene, xylene; halogenated saturated hydrocarbons, such as
carbon tetrachloride, chloroform, dichloromethane, chlorobutane,
bromobutane, chloropentane, bromopentane, chlorohexane,
bromohexane, chlorocyclohexane, and bromocyclohexane; halogenated
unsaturated hydrocarbons, such as chlorobenzene, dichlorobenzene,
and trichlorobenzene; alcohols, such as methanol, ethanol,
propanol, isopropanol, butanol, t-butyl alcohol; carboxylic acids,
such as, formic acid, acetic acid, and propionic acid; ethers, such
as, dimethyl ether, diethyl ether, methyl-t-butyl ether,
tetrahydrofuran, tetrahydropyran, and dioxane; amines, such as
trimethylamine, triethylamine,
N,N,N',N'-tetramethylethylenediamine, and pyridine; amides, such
as, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethyl
acetamide, N-methylmorpholine oxide, and N-methyl-2-pyrrolidone.
These may be used alone or a mixture thereof.
[0135] As the base used for reaction, exemplified are: lithium
hydride, sodium hydride, potassium hydride, methyl lithium, n-butyl
lithium, t-butyl lithium, phenyl lithium, lithium diisopropyl
amide, lithium hexamethyldisilazide, sodium hexa methyldisilazide,
potassium hexamethyl disilazide, etc.
[0136] After the reaction, it can be obtained by a usual
post-treatment, for example, quenching with water, then extracting
by an organic solvent, and distilling of the solvent.
[0137] Isolation and purification of the product can be performed
by a method, such as recrystallization, distillation, or
fractionation by chromatography.
[0138] Next, the use of the polymer of the present invention is
explained.
[0139] The polymer of the present invention has strong
fluorescence, and it can be used as a polymeric fluorescent
substance. Moreover, since the luminescence from a thin film is
used, polymeric fluorescent substances having fluorescence in the
solid state are used preferably. Moreover, the polymer has
excellent electronic transporting property, and can be used
suitably as a polymer LED material, or a charge transporting
material. The polymer of the present invention can be used also as
a material for electronic devices, and can be used also as a
coloring matter for lasers, a solar-battery material, an organic
semiconductor for organic transistors, and a conductive thin-film
material.
[0140] Next, the polymer LED of the present invention will be
described. The polymer LED of the present invention, has a
light-emitting layer between an anode and a cathode, and the
polymer-of the present invention is contained in the light-emitting
layer.
[0141] As the polymer LED of the present invention, there are
listed polymer LEDs having an electron transporting layer disposed
between a cathode and a light emitting layer, polymer LEDs having a
hole transporting layer disposed between an anode and a light
emitting layer, polymer LEDs having an electron transporting layer
disposed between a cathode and a light emitting layer and having a
hole transporting layer disposed between an anode and a light
emitting layer.
[0142] Moreover, as the polymer LED of the present invention, there
are exemplified: a device having a layer containing a conducting
polymer disposed between at least one of the electrodes and a light
emitting layer, adjacently to said electrode; and a device having
an insulating layer having a thickness of 2 nm or less disposed
between at least one of the electrodes and a light emitting layer,
adjacently to said electrode.
[0143] For example, the following structures a) to d) are
specifically exemplified.
[0144] a) anode/light emitting layer/cathode
[0145] b) anode/hole transporting layer/light emitting
layer/cathode
[0146] c) anode/light emitting layer/electron transporting
layer//cathode
[0147] d) anode/hole transporting layer/light emitting
layer/electron transporting layer/cathode
[0148] (wherein, "/" indicates adjacent lamination of layers.)
[0149] 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 may
also each independently used in two or more layers.
[0150] Of 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.
[0151] For enhancing adherence with an electrode and improving
charge injection from an electrode, the above 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.
[0152] 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.
[0153] 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.
[0154] For example, the following structures e) to p) are
specifically exemplified.
[0155] e) anode/charge injecting layer/light emitting
layer/cathode
[0156] f) anode/light emitting layer/charge injecting
layer/cathode
[0157] g) anode/charge injecting layer/light emitting layer/charge
injecting layer/cathode
[0158] h) anode/charge injecting layer/hole transporting
layer/light emitting layer/cathode
[0159] i) anode/hole transporting layer/light emitting layer/charge
injecting layer/cathode
[0160] j) anode/charge injecting layer/hole transporting
layer/light emitting layer/charge injecting layer/cathode
[0161] k) anode/charge injecting layer/light emitting
layer/electron transporting layer/cathode
[0162] l) anode/light emitting layer/electron transporting
layer/charge injecting layer/cathode
[0163] m) anode/charge injecting layer/light emitting
layer/electron transporting layer/charge injecting
layer/cathode
[0164] n) anode/charge injecting layer/hole transporting
layer/light emitting layer/electron transporting layer/cathode
[0165] o) anode/hole transporting layer/light emitting
layer/electron transporting layer/charge injecting
layer/cathode
[0166] p) anode/charge injecting layer/hole transporting
layer/light emitting layer/electron transporting layer/charge
injecting layer/cathode
[0167] 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, and the like.
[0168] When the above 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.
[0169] 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.
[0170] Regarding the kind of an ion to be doped, an anion is used
for a hole injecting layer and a cation is used for 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.
[0171] The thickness of the charge injecting layer is for example,
from 1 nm to 100 nm, preferably from 2 nm to 50 nm.
[0172] Materials used in the charge injecting layer may be selected
appropriately according to the relation with the electrode
materials 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.
[0173] The insulation layer having a thickness of 2 nm or less has
function to make charge injection easy. As the material of the
above 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.
[0174] Specifically, there are listed the following structures q)
to ab) for example.
[0175] q) anode/insulation layer having a thickness of 2 nm or
less/light emitting layer/cathode
[0176] r) anode/light emitting layer/insulation layer having a
thickness of 2 nm or less/cathode
[0177] 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
[0178] t) anode/insulation layer having a thickness of 2 nm or
less/hole transporting layer/light emitting layer/cathode
[0179] u) anode/hole transporting layer/light emitting
layer/insulation layer having a thickness of 2 nm or
less/cathode
[0180] 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
[0181] w) anode/insulation layer having a thickness of 2 nm or
less/light emitting layer/electron transporting layer/cathode
[0182] x) anode/light emitting layer/electron transporting
layer/insulation layer having a thickness of 2 nm or
less/cathode
[0183] 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
[0184] z) anode/insulation layer having a thickness of 2 nm or
less/hole transporting layer/light emitting layer/electron
transporting layer/cathode
[0185] aa) anode/hole transporting layer/light emitting
layer/electron transporting layer/insulation layer having a
thickness of 2 nm or less/cathode
[0186] 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
[0187] In producing a polymer LED, when a film is formed from a
solution by using such polymer soluble in an organic solvent, only
required is removal of the solvent by drying after coating of this
solution, and even in the case of mixing of a charge transporting
material and a light emitting material, the same method can be
applied, causing an extreme advantage in production. 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.
[0188] Regarding the thickness of the light emitting 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 for example, it is from 1 nm
to 1 .mu.m, preferably from 2 nm to 500 nm, further preferably from
5 nm to 200 nm.
[0189] In the polymer LED of the present invention, light emitting
materials other than the above polymeric fluorescent substance can
also be mixed in a light emitting layer. Further, in the polymer
LED of the present invention, the light emitting layer containing
light emitting materials other than the above polymeric fluorescent
substance may also be laminated with a light emitting layer
containing the above polymeric fluorescent substance.
[0190] As the light emitting material, known materials can be used.
In a compound having lower molecular weight, there can be used, for
example, naphthalene derivatives, anthracene or derivatives
thereof, perylene or derivatives thereof; dyes such as polymethine
dyes, xanthene dyes, coumarine dyes, cyanine dyes; metal complexes
of 8-hydroxyquinoline or derivatives thereof, aromatic amine,
tetraphenylcyclopentane or derivatives thereof, or
tetraphenylbutadiene or derivatives thereof, and the like.
[0191] Specifically, there can be used known compounds such as
those described in JP-A Nos. 57-51781, 59-195393 and the like, for
example.
[0192] 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.
[0193] 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.
[0194] 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-thienyleneviny- lene) 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.
[0195] Polyvinylcarbazole or derivatives thereof are obtained, for
example, by cation polymerization or radical polymerization from a
vinyl monomer.
[0196] 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.
[0197] As the polysiloxane or derivatives thereof, those having the
structure of the above 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.
[0198] 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.
[0199] 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.
[0200] 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.
[0201] 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.
[0202] 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.
[0203] 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, anthraquinonedimethane 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, or metal complexes of
8-hydroxyquinoline or derivatives thereof, polyquinoline and
derivatives thereof, polyquinoxaline and derivatives thereof,
polyfluorene or derivatives thereof, and the like.
[0204] 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.
[0205] 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)aluminu- m and polyquinoline are further
preferable.
[0206] 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. At
the time of film forming from a solution or a molten state, a
polymer binder can be used together.
[0207] 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.
[0208] 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.
[0209] 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.
[0210] 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.
[0211] 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.
[0212] In the present invention, at least one of an anode or a
cathode is transparent or semitransparent, and it is preferable
that the anode is transparent or semitransparent. 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 films (NESA and the like) fabricated by using an electron
conductive glass composed of indium-tin-oxide (ITO), indium zinc
oxide and the like, which are metal oxide complexes, and gold,
platinum, silver, copper and the like are used, and 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.
[0213] 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.
[0214] 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.
[0215] 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.
[0216] 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.
[0217] 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.
[0218] As the protective layer, there can be used a polymer, 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 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.
[0219] The polymer LED of the present invention can be suitably
used as a flat light source, segment display apparatus, dot-matrix
display apparatus, and back light of a liquid crystal display.
[0220] 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 are a
method in which a mask with a window in pattern form is placed on
the above 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 polymers 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.
[0221] Further, the above 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.
EXAMPLES
[0222] Hereafter, examples are shown in order to explain the
present invention in detail, but the present invention should not
be construed to be limited thereto.
[0223] In the examples, the number average molecular weight and the
weight average molecular weight were determined by gel permeation
chromatography (GPC) using chloroform solvent as the polystyrene
reduced number average molecular weight and the weight average
molecular weight, respectively.
Synthetic Example 1
[0224] <Synthesis of
2,2'-dibromo-5,5'-dioctyloxy-1,1'-biphenyl> 66
[0225] 3,3'-dioctyloxy-1,1'-biphenyl which is a raw material was
synthesized by Yamamoto coupling, after dioctylation of
3-bromophenol in ethanol.
[0226] The above 3,3'-dioctyloxy-1,1'-biphenyl 133 g was dissolved
in dried N,N-dimethylformamide 1820 ml. At 0.degree. C. (dry
ice-methanol bath), a solution of N-bromosuccinimide 117.5
g/N,N-dimethylformamide 910 ml was added dropwise for 60 minutes.
After the dropwise adding, the reaction liquid was brought back to
a room temperature and stirred overnight. The reaction liquid was
charged into water and extracted with n-hexane, and then the
solvent was distilled off and 179 g of crude product was
obtained.
[0227] ecrystallization was repeated using 2-propanol, and 122 g of
2,2'-dibromo-5,5'-dioctyloxy-1,1'-biphenyl was obtained.
[0228] .sup.1H-NMR (300 MHz/CDCl.sub.3):
[0229] .delta. (ppm)=0.88 [t, 6H], 1.2.about.1.8 [m, 24H], 3.95 [t,
4H], 6.7.about.6.8 [m, 4H], 7.52 [d, 2H]
Synthetic Example 2
[0230] <Synthesis of
2,2'-di-iodo-5,5'-dioctyloxy-1,1'-biphenyl> 67
[0231] Flaky magnesium 4.05 g was put in a 500 ml three-necked
flask under nitrogen atmosphere. Tetrahydrofuran solution 200 ml of
the above 2,2'-dibromo-5,5.sup.1-dioctyloxy-1,1.sup.1-biphenyl 45 g
was prepared in another flask, and 20 ml of the solution was added
in the flask containing magnesium. Five drops of 1,2-dibromoethane
as the initiator was added, and heated. When the exothermic
reaction started, the remaining solution was added dropwise for 30
minutes. After the dropwise addition, the reaction was conducted
for 1 hour with refluxing. Then, it was cooled to 0.degree. C., and
tetrahydrofuran 150 ml solution of iodine 44.2 g was added
dropwise. After the dropwise adding, the reaction liquid was
stirred overnight.
[0232] The reaction liquid was charged into water and extracted
with chloroform, and washed with sodium-thiosulfate aqueous
solution and saturated NaCl aqueous solution. After being dried
with sodium sulfate, the solvent was distilled off, and 53 g of
crude product was obtained.
[0233] By recrystallization using 2-propanol, 43 g of
2,2'-di-iodo-5,5'-dioctyloxy-1,1'-biphenyl was obtained.
[0234] .sup.1H-NMR (200 MHz/CDCl.sub.3):
[0235] .delta. (ppm)=0.90 [t, 6H], 1.2.about.1.8 [m, 24H], 3.93 [t,
4H], 6.6.about.6.8 [m, 4H], 7.74 [d, 2H]
[0236] MS(APCI(+)):M.sup.+ 662
Synthetic Example 3
[0237] <Synthesis of
4,4'-dibromo-2,2'-di-iodo-5,5'-dioctyloxy-1,1'-bip- henyl>
68
[0238] The above 2,2'-di-iodo-5,5'-dioctyloxy-1,1'-biphenyl 37 g
was charged into 1L flask under nitrogen atmosphere, and trimethyl
phosphate 800 ml was added and dissolved. Iodine 10.6 g was further
added, trimethyl phosphate 70 ml of bromine 19 g was added
dropwise. After stirring for 4 hours, trimethyl phosphate 35 ml of
bromine 9.5 g was added dropwise. Then, it was stirred overnight.
The reaction liquid was charged into water and extracted with
chloroform, and washed with sodium-thiosulfate aqueous solution and
saturated NaCl aqueous solution. After being dried with sodium
sulfate, the solvent was distilled off, and 46 g of crude product
was obtained. By purification using silica gel chromatography
(cyclohexane:toluene=20:1), 4,4'-dibromo-2,2'-di-iodo-5,5'-
-dioctyloxy-1,1'-biphenyl 20.5 g was obtained.
[0239] .sup.1H-NMR (200 MHz/CDCl.sub.3):
[0240] .delta. (ppm)=0.88 [t, 6H], 1.2.about.1.9 [m, 24H], 3.99 [m,
4H], 6.70 [s, 2H], 8.03 [s, 2H]
[0241] MS(APCI(+)):M.sup.+ 820
Synthetic Example 4
[0242] Synthesis of Compound A 69
[0243] The above
4,4'-dibromo-2,2'-di-iodo-5,5'-dioctyloxy-1,1'-biphenyl 1.00 g
(appearance mole number 1.22 mmols) was put in a 100 ml
three-necked flask which was flame dried and argon gas substituted,
and dissolved in dehydrated diethyl ether 10 ml. This solution was
cooled to -90.degree. C. by methanol/liquid nitrogen, and n-BuLi
1.7 ml (1.6M n-hexane solution, 2.7 mmol) was added dropwise. After
keeping the temperature for 1 hour, diethyl-ether solution (5 ml)
of dichlorophenyl phosphine (0.22 g, 1.22 mmol) was added dropwise.
After having temperature raised to a room temperature and stirring
for 15 hours, it was cooled at 0.degree. C. and 5% NaHCO.sub.3
aqueous solution was added dropwise. The aqueous phase was
extracted with toluene, the organic layer was collected, and washed
with water and then saturated NaCl aqueous solution. The solvent
was distilled off and 1.11 g of crude product was obtained. By
purification using Silica gel column chromatography (eluent
hexane:ethylacetate=100:1 (0.1% triethylamine)), and Compound A was
obtained in 0.52 g (purity 96.1% and yield 68.5%).
[0244] .sup.1H-NMR (CDCl.sub.3,300 MHz):
[0245] .delta. 7.77 (d, 2H), 7.31-7.13 (m, 7H), 4.198t, 4H),
1.96-1.87 (m, 4H), 1.69-1.52 (m, 4H), and 1.35-1.26 (m, 16H) and
0.90 (t, 6H)
Synthetic Example 5
[0246] Synthesis of Compound B 70
[0247] The above
4,4'-dibromo-2,2'-di-iodo-5,5'-dioctyloxy-1,1'-biphenyl 5.00 g
(apparent mole number 6.1 mmols) was put in a 300 ml three-necked
flask which was flame dried and argon gas substituted, and
dissolved in dehydrated diethyl ether 50 ml. This solution was
cooled to -90.degree. C. by methanol/liquid nitrogen, and n-BuLi
8.4 ml (1.6M n-hexane solution, 13.4 mmol) was added dropwise.
After keeping the temperature for 1 hour, sulfur 0.20 g (6.1 mmol)
was added. After having the temperature raised to a room
temperature, and stirring for 3.5 hours, sulfur 2.00 g (61 mmol)
was added and stirred further 4 hours. Then, it was cooled at
0.degree. C. and 15 ml of 1N hydrochloric acid was added dropwise.
The aqueous phase was extracted with diethylehter, the organic
layer was collected, and washed with water and then saturated NaCl
aqueous solution. After being dried with sodium sulfate, the
solvent was distilled off and 6.26 g of crude product was obtained.
By purification using Silica gel column chromatography (eluent
hexane:ethylacetate=20:1), and Compound B was obtained in 0.91 g
(p. 87.3%, y.20.7%).
[0248] .sup.1H-NMR (CDCl.sub.3,300 MHz):
[0249] .delta. 7.69 (s, 2H), 7.08 (s, 2H), 4.09 (t, 4H), 1.92-1.81
(m, 4H), 1.58-1.26 (m, 20H), 0.88 (t, 6H)
Synthetic Example 6
[0250] Synthesis of Compound C 71
[0251] The above
4,4'-dibromo-2,2'-di-iodo-5,5'-dioctyloxy-1,1'-biphenyl 5.0 g was
charged into a 100 ml flask under nitrogen atmosphere, and
tetrahydrofuran 50 ml was added to dissolve it. It was cooled at
90.degree. C. and 8.4 ml of N-Butyl Lithium/1.6M-hexane solution
was added dropwise. After 1.5 hours stirring, tetrahydrofuran
solution 61 g of magnesium-bromide 3.38 g was added, and raised the
temperature to a room temperature, and further stirred for 1.5
hours. It was cooled to -90.degree. C. again, and
1,2-dichlorotetramethyl disilane 1.60 g was added. Then the
temperature was raised and reacted for 8.5 hours with
refluxing.
[0252] After having distilled off the solvent, toluene 100 ml was
charged and stirred, and then insoluble matters were filtrated. The
solvent was distilled off again and a crude product was obtained.
The crude product was purified by silica gel chromatography (eluent
hexane:triethylamine toluene=800:5), and 0.24 g of Compound C was
obtained.
[0253] .sup.1H-NMR (300 MHz/CDCl.sub.3):
[0254] .delta. (ppm)=0.20 [s, 12H], 0.89 [t, 6H], 1.1.about.1.6 [m,
20H], 1.89 [m, 4H], 4.08 [t, 4H], 6.92 [s, 2H], 7.57 [s, 2H]
Synthetic Example 7
[0255] Synthesis of Compound D 72
[0256] In an inert atmosphere, 3-bromophenol 90 g was dissolved in
ethanol 600 ml. 39 g of potassium hydroxide was added further, and
dissolved at 70.degree. C. 1-bromo-3,7-dimethyloctane 126 g was
added dropwise from a dropping funnel for 15 minutes. After the
dropwise adding, the temperature was raised to 84.degree. C., and
stirring with heating was carried out for about 22 hours.
[0257] After the heating, it was standing to cool to a room
temperature. The reaction liquid was divided into two portions,
each of which was added into 500 ml of water, and ethanol was
distilled off with using evaporator. After distilling off the
ethanol, the residual solutions were collected together and into
three portions. To each of the portions, 300 ml of ethyl acetate
was added and partitioned, respectively, and the organic layer was
washed with 200 ml of water twice. After having collected the
organic layers and distilling off the solvent using an evaporator,
drying was carried out at 90.degree. C. for 5 hours under reduced
pressure using a rotary pump. About 150 g of
3-(3,7-dimethyloctyloxy)-bromobenzene was obtained as an oily
product. Dried tetrahydrofuran 100 ml, magnesium 7.5 g and small
quantity of iodine were charged into a three-necked flask under an
inert atmosphere. Using a dropping funnel, the above
3-(3,7-dimethyloctyloxy)-bromobenzene 90 g was added dropwise for
50 minutes. After the dropwise adding, dried tetrahydrofuran 200 ml
was added and heat-stirring was carried out for 2 hours with
refluxing to prepare a Grignard reagent. After the heating, it was
left standing to cool to a room temperature. Trimethyl borate 38 g
and dried tetrahydrofuran 300 ml were charged into another
three-necked flask, and the flask was cooled by a dry ice-acetone
bath. Using a dropping funnel, the above Grignard reagent solution
was added dropwise for 35 minutes. After the dropwise adding the
reaction liquid was heated to a room temperature. After having
added the reaction liquid to a dilute sulfuric acid (sulfuric acid
12 ml/water 360 ml) and stirring, it was divided into two portions,
and each of them was extracted with 150 ml and 100 ml of ethyl
acetate. The organic layers were collected together and divided
into three portions, and each of them was washed with 100 ml of
water. The organic layers after washing were collected together and
the solvent was distilled off using an evaporator. A suspension of
the solid content was produced by adding 100 ml of hexane and
filtrated. Further, it washed with 100 ml of hexane. White solid of
3-(3,7-dimethyloctyloxy)-- phenyl boric acid 63 g was obtained.
Under an inert atmosphere, to a three-necked flask, the above
3-(3,7-dimethyloctyloxy)-bromobenzene 60 g, toluene 250 ml, water
250 ml, potassium carbonate 62 g and tetrakis
(triphenylphosphine)palladium complex 1.2 g were charged. After
bubbling of the solution with argon for 20 minutes to deaerate
oxygen, the above 3-(3,7-dimethyloctyloxy)-phenyl boric acid 63 g
was added, the temperature was raised to 90.degree. C., and
stirring with heating was carried out for 8 hours. After the
heating, it was left to stand for cooling to a room temperature.
After partitioning the toluene layer, coloring components were
removed with silica gel chromatography. The solvent was distilled
off and 98 g of Compound D was obtained as an oily product.
[0258] .sup.1H-NMR (200 MHz/CDCl.sub.3):
[0259] (ppm)=0.87 [d, 12H], 0.94 [d, 6H], 1.1.about.1.8 [m, 20H],
4.0 4 [t, 4H], 6.88 [d, 2H], 7.1.about.7.3 [m, 4H], 7.32 [t,
2H]
Synthetic Example 8
[0260] Synthesis of Compound E 73
[0261] The above compound D 20 g was dissolved in dried
N,N-dimethylformamide 400 ml. A solution of N-bromosuccinimide 15.5
g/N,N-dimethylformamide 300 ml was added dropwise for 90 minutes
with ice cooling. After the dropwise adding, the ice bath was
removed and stirred overnight. After distilling off the solvent, it
was dissolved in toluene 200 ml, and washed with 200 ml of water 3
times, and the solvent was distilled off. 26 g of oily product was
obtained. From the measurement result of a LC-MS spectrum, isomers
having different bromo substituted positions were observed, and the
purity of Compound E was about 65% (LC area percentage).
[0262] .sup.1H-NMR (200 MHz/CDCl.sub.3):
[0263] (ppm)=0.86[d, 12H], 0.93[d, 6H], 1.1.about.1.8 [m, 20H],
3.97[t, 4H], 6.79[d, 2H], 6.82[d, 2H], 7.52[d, 2H]
[0264] MS(APCI (+)):M.sup.+ 624
Synthetic Example 9
[0265] Synthesis of Compound F 74
[0266] In a 200 ml four-necked flask whose inside atmosphere was
replaced with argon, Compound E 5.00 g (8.0 mmol) was dissolved in
80 ml dehydrated ether, and cooled to -78.degree. C. To this
solution, n-butyllithium 11 ml (17.6 mmol, 1.6M hexane solution)
was added dropwise, and stirred for 3.5 hours. This solution was
added dropwise to an ether solution 500 ml of tetrachlorosilane
25.8 g (152 mmol) cooled at -78.degree. C. After stirring for 1
hour, the temperature was raised to a room temperature, and it was
stirred for 15 hours. The reaction liquid was filtered under argon
atmosphere, and the filtrate was condensed to give a crude product
4.52 g. The resultant crude product was put into a 500 ml
three-necked flask whose inside was replaced with argon gas, and
dissolved in 90 ml dehydrated ether, and cooled to -78.degree. C.
Phenyl lithium 23 ml (24 mmol, 1.06M cyclopentane/ether solution)
was added dropwise to this solution. After stirring for 20 minutes,
it was raised to a room temperature and stirred for 4 hours. Water
was added and partitioned and the aqueous layer was extracted with
diethyl ether. The organic layers were collected together and
washed with saturated sodium hydrogencarbonate aqueous solution and
saturated NaCl aqueous solution. After drying with sodium
hydrogensulfate, the solvent was distilled off, and 6.66 g of a
crude product of Compound F was obtained.
[0267] 0.86 (d, 12H), 0.97 (d, 6H), 1.16.about.1.90 (m, 20H), 4.09
(br, 4H), 6.84.about.6.88 (m, 2H), 7.29.about.7.66 (m, 28H)
[0268] MS(APCI(+)):M.sup.+ 647.4
Synthetic Example 10
[0269] Synthesis of Compound G 75
[0270] In a 300 ml three-necked flask whose inside atmosphere was
replaced with argon, Compound F 5.00 g (purity 85.1%, 6.6 mmol) was
put in and dissolved in dehydrated DMF65 ml. N-bromosuccinimide
2.45 g (13.8 mmol) was charged to this solution. After stirring at
a room temperature for 5 hours, it was extracted with hexane (80
mlx5) in a glove box. The solvent was distilled off, and 14.02 g of
a crude product (LC area percentage 19.9% including DMF) was
obtained. After separation with reversed-phase silica gel column
chromatography (acetonitrile:toluene=20:1), fractions were
extracted with hexane (in order to remove a minute amount of acetic
acid in acetonitrile), and washed by 5% sodium-hydrogencarbonate
aqueous solution and saturated NaCl aqueous solution. After drying
with sodium sulfate, the solvent was distilled off, and 0.30 g (LC
area percentage 58%, yield 3.3%) of Compound G was obtained.
[0271] .sup.1H-NMR (300 MHz/acetone-d6):
[0272] .delta. 0.86 (d, 12H), 0.99 (d, 6H), 1.17.about.1.95 (m,
20H), 4.31 (br, 4H), 7.37.about.7.50 (m, 2H), 7.68.about.7.71 (m,
28H), 7.81 (s, 2H), 8.00 (s, 2H)
[0273] MS(APCI(+)):M.sup.+ 804.9
Synthetic Example 11
[0274] Synthesis of Compound H 76
[0275] Compound F 3.91 g (purity 85.1%, 5.1 mmol) was put in a 200
ml three necked flask whose inside was replaced with argon gas, and
dissolved in dehydrated DMF 50 ml. NCS 1.47 g (10.8 mmol) was
charged into this solution. NCS was added, with pursuing the
reaction by LC. (total 2.62 g). After stirring for 60 hours at a
room temperature, it was extracted with hexane (100 mlx5) in a
glove box. The solvent was distilled off, and 12.73 g (LC area
percentage 34.1%, including DMF) of a crude product was obtained.
After separation with reversed-phase silica gel column
chromatography (acetonitrile:toluene=20:1), the fractions were
extracted with hexane, and washed with 5% sodium-hydrogencarbonate
aqueous solution and saturated NaCl aqueous solution (in order to
remove the minute amount of acetic acid in acetonitrile). After
drying with sodium sulfate, the solvent was distilled off, and 0.18
g (82.5% of LC area percentage, 3.6% of yield) Compound H was
obtained.
[0276] .sup.1H-NMR (300 MHz/acetone-d6):
[0277] .delta. 0.87 (d, 12H), 0.99 (d, 6H), 1.10.about.1.94 (m,
20H), 4.28 (b r, 4H), 7.30.about.7.71 (m, 10H), 7.83 (br, 4H)
[0278] MS(APCI(+)):M.sup.+ 715.3
Example 1
Condensation Polymerization of Compound A
[0279] <Synthesis of Polymer 1>
[0280] Compound A 0.59 g,
N,N'-bis(4-bromophenyl)-N,N'-bis(4-n-butyl
phenyl)-1,4-phenylenediamine 0.26 g, 2,2'-bipyridyl 0.48 g were
charged into a reaction vessel, and the atmosphere of the reaction
system was replaced with nitrogen gas. To this, 35 ml of
tetrahydrofuran (dehydrated solvent) which was deaerated beforehand
by bubbling with argon gas was added. Next, bis(1,5-cyclo
octadiene) nickel (0) 0.85 g was added to this mixed solution, and
reacted at 60.degree. C. for 3 hours. The reaction was performed in
nitrogen-gas atmosphere. After the reaction, this solution was
cooled and then poured into a mixed solution of 25% aqueous-ammonia
10 ml/methanol 120 ml/ion-exchanged water 50 ml, and stirred for
about 1 hour. Next, resulting precipitate was collected by
filtration. The precipitate was washed with ethanol, and dried at a
reduced pressure for 2 hours. Next, this precipitate was dissolved
in toluene 30 mL, after the addition of 1N hydrochloric-acid 30 mL,
it was stirred for 1 hour. The aqueous layer was removed, and 4%
aqueous-ammonia 30 mL was added to an organic layer, and after
stirring for 1 hour, the aqueous layer was removed. The organic
layer was added dropwise to methanol 200 mL, and stirred for 1
hour. The deposited precipitate was filtered and dried for 2 hours
at a reduced pressure, and then dissolved in toluene 30 mL. Then,
it was purified by passing through alumina column (20 g of
alumina). The collected toluene solution was added dropwise to
methanol 250 mL, stirred for 1 hour, and deposited precipitate was
filtered and dried for 2 hours at a reduced pressure. The yield of
the resulting polymer was 0.06 g. This polymer is referred to as
Polymer 1.
[0281] The polystyrene reduced number average molecular weight of
Polymer 1 was 5.0.times.10.sup.2, and the polystyrene reduced
weight average molecular weight was 6.2.times.10.sup.3.
Example 2
Condensation Polymerization of Compound B
[0282] <Synthesis of Polymer 2>
[0283] Compound B 0.35 g,
N,N'-bis(4-bromophenyl)-N,N'-bis(4-n-butyl
phenyl)-1,4-phenylenediamine 0.16 g, 2,2'-bipyridyl 0.37 g were
charged into a reaction vessel, and the atmosphere of the reaction
system was replaced with nitrogen gas. To this, 28 ml of
tetrahydrofuran (dehydrated solvent) which was deaerated beforehand
by bubbling with argon gas was added. Next, bis(1,5-cyclo
octadiene) nickel (0) 0.70 g was added to this mixed solution, and
reacted at 60.degree. C. for 3 hours. The reaction was performed in
nitrogen-gas atmosphere. After the reaction, this solution was
cooled and then poured into a mixed solution of 25% aqueous-ammonia
10 ml/methanol 120 ml/ion-exchanged water 50 ml, and stirred for
about 1 hour. Next, resulting precipitate was collected by
filtration. The precipitate was washed with ethanol, and dried at a
reduced pressure for 2 hours. Next, this precipitate was dissolved
in toluene 30 mL, after the addition of 1N hydrochloric-acid 30 mL,
it was stirred for 1 hour. The aqueous layer was removed, and 4%
aqueous-ammonia 30 mL was added to an organic layer, and after
stirring for 1 hour, the aqueous layer was removed. The organic
layer was added dropwise to methanol 200 mL, and stirred for 1
hour. The deposited precipitate was filtered and dried for 2 hours
at a reduced pressure, and then dissolved in toluene 30 mL. Then,
it was purified by passing through alumina column (20 g of
alumina). The collected toluene solution was added dropwise to
methanol 250 mL, stirred for 1 hour, and deposited precipitate was
filtered and dried for 2 hours at a reduced pressure. The yield of
the resulting polymer was 0.13 g. This polymer is referred to as
Polymer 2.
[0284] The polystyrene reduced number average molecular weight of
Polymer 2 was 6.2.times.10.sup.3, and the polystyrene reduced
weight average molecular weight was 5.1.times.10.sup.4.
Example 3
Condensation Polymerization of Compound C
[0285] <Synthesis of Polymer 3>
[0286] Compound C 0.30 g,
N,N'-bis(4-bromophenyl)-N,N'-bis(4-n-butyl
phenyl)-1,4-phenylenediamine 0.13 g, 2,2'-bipyridyl 0.30 g were
charged into a reaction vessel, and the atmosphere of the reaction
system was replaced with nitrogen gas. To this, 20 ml of
tetrahydrofuran (dehydrated solvent) which was deaerated beforehand
by bubbling with argon gas was added. Next, bis(1,5-cyclo
octadiene) nickel (0) 0.52 g was added to this mixed solution, and
reacted at 60.degree. C. for 3 hours. The reaction was performed in
nitrogen-gas atmosphere. After the reaction, this solution was
cooled and then poured into a mixed solution of 25% aqueous-ammonia
10 ml/methanol 120 ml/ion-exchanged water 50 ml, and stirred for
about 1 hour. Next, resulting precipitate was collected by
filtration. The precipitate was washed with ethanol, and dried at a
reduced pressure for 2 hours. Next, this precipitate was dissolved
in toluene 30 mL, after the addition of 1N hydrochloric-acid 30 mL,
it was stirred for 1 hour. The aqueous layer was removed, and 4%
aqueous-ammonia 30 mL was added to an organic layer, and after
stirring for 1 hour, the aqueous layer was removed. The organic
layer was added dropwise to methanol 200 mL, and stirred for 1
hour. The deposited precipitate was filtered and dried for 2 hours
at a reduced pressure, and then dissolved in toluene 30 mL. Then,
it was purified by passing through alumina column (20 g of
alumina). The collected toluene solution was added dropwise to
methanol 250 mL, stirred for 1 hour, and deposited precipitate was
filtered and dried for 2 hours at a reduced pressure. The yield of
the resulting polymer was 0.11 g. This polymer is referred to as
Polymer 3.
[0287] The polystyrene reduced number average molecular weight of
Polymer 3 was 1.4.times.10.sup.3, and the polystyrene reduced
weight average molecular weight was 4.9.times.10.sup.4.
Example 4
Condensation Polymerization of Compound G
[0288] <Synthesis of Polymer 4>
[0289] Compound G 0.20 g,
N,N'-bis(4-bromophenyl)-N,N'-bis(4-n-butyl
phenyl)-1,4-phenylenediamine 0.07, 2,2'-bipyridyl 0.17 g were
charged into a reaction vessel, and the atmosphere of the reaction
system was replaced with nitrogen gas. To this, 20 ml of
tetrahydrofuran (dehydrated solvent) which was deaerated beforehand
by bubbling with argon gas was added. Next, bis(1,5-cyclo
octadiene) nickel (0) 0.3 g was added to this mixed solution, and
stirred at a room temperature for 10 minutes, and reacted at
60.degree. C. for 3 hours. The reaction was performed in
nitrogen-gas atmosphere. After the reaction, this solution was
cooled and then poured into a mixed solution of methanol 120
ml/ion-exchanged water 200 ml, and stirred for about 1 hour. Next,
resulting precipitate was collected by filtration. The precipitate
was dried and dissolved in chloroform. The solution was filtered to
remove insoluble matters, and the chloroform was distilled off to
give a solid product. This solid product was washed with methanol
and dried at a reduced pressure to yield a polymer 0.08 g. This
polymer is referred to as Polymer 4.
[0290] The polystyrene reduced number average molecular weight of
Polymer 4 was 1.5.times.10.sup.3, and the polystyrene reduced
weight average molecular weight was 5.0.times.10.sup.3.
Example 5
Polymerization of Compound H)
[0291] <Synthesis of Polymer 5>
[0292] Compound H 0.21 g,
N,N'-bis(4-bromophenyl)-N,N'-bis(4-n-butyl
phenyl)-1,4-phenylenediamine 0.10, 2,2'-bipyridyl 0.27 g were
charged into a reaction vessel, and the atmosphere of the reaction
system was replaced with nitrogen gas. To this, 20 ml of
tetrahydrofuran (dehydrated solvent) which was deaerated beforehand
by bubbling with argon gas was added. Next, bis(1,5-cyclo
octadiene) nickel (0) 0.5 g was added to this mixed solution, and
stirred at a room temperature for 10 minutes, and reacted at
60.degree. C. for 3 hours. The reaction was performed in
nitrogen-gas atmosphere. After the reaction, this solution was
cooled and then poured into a mixed solution of methanol 100
ml/ion-exchanged water 200 ml, and stirred for about 1 hour. Next,
resulting precipitate was collected by filtration. The precipitate
was dried and dissolved in toluene. The solution was filtered to
remove insoluble matters, and the toluene was distilled off to give
a solid product. This solid product was washed with ethanol and
dried at a reduced pressure to yield a polymer 0.09 g. This polymer
is referred to as Polymer 5.
[0293] The polystyrene reduced number average molecular weight of
Polymer 5 was 1.6.times.10.sup.3, and the polystyrene reduced
weight average molecular weight was 5.4.times.10.sup.3.
Example 6
[0294] <Fluorescence Characteristics>
[0295] Each of the 2 wt % chloroform solutions of Polymers 1 to 5
were spin coated respectively on quartz, and thin films of
polymeric fluorescent substance were produced. The fluorescence
spectrum of these thin films were measured using a
spectrophotometer (Hitachi 850). All of them have strong
fluorescence and they respectively showed fluorescence peak
wavelengthes shown in Table 1.
1 TABLE 1 Fluorescence peak wavelength Polymer (nm) Polymer 1 516
Polymer 2 468 Polymer 3 458 Polymer 4 466 Polymer 5 458
CALCULATION EXAMPLES
[0296] Calculation examples of bond-distance ratio are shown below.
The calculation was performed using Gaussian 98 (b3lyp/6-31g*).
Calculation Example 1
[0297] Comparison of a Monomer with a Trimer
[0298] The bond-distance ratio of a monomer having hydrogen atoms
at the bonding positions in polymerization was compared with that
of the trimer.
2 77 78 Calculation compound Bond-distance ratio Calculation
compound 1 1.254 Calculation compound 2 (Center) 1.256 Calculation
compound 2 (Terminal) 1.254
[0299] The difference of the bond-distance ratios was small, and
the bond-distance ratio of a polymer can be approximated by that of
the monomer having hydrogen atoms at the bonding position in
polymerization.
Calculation Example 2
[0300] Comparison of the Side Chains
[0301] The bond-distance ratios were compared between a compound
having methoxy group as the alkyloxy group side chain and a
compound having n-octyloxy group.
3 79 80 Calculation compound Bond-distance ratio Calculation
compound 3 1.254 Calculation compound 4 1.254
[0302] The difference of the bond-distance ratios was small, and
the bond-distance ratio of a compound having n-octyloxy group can
be approximated by that of the compound having methoxy group.
Calculation Example 3
[0303] Calculation of the Compounds Produced in Examples
4 81 82 83 84 85 86 In the formula, Ph represents a phenyl group.
Calculation compound Bond-distance ratio Calculation compound 5
1.329 Calculation compound 6 1.304 Calculation compound 7 1.338
Calculation compound 8 1.268 Comparative Example 1 1.085
Comparative Example 2 1.071
[0304] The polymer of the present invention is a new polymer which
can be used as a light-emitting material, a charge transporting
material, etc.
* * * * *