U.S. patent application number 10/994320 was filed with the patent office on 2005-03-24 for luminescent device material, luminescent device using the same, and amine compound.
This patent application is currently assigned to FUJI PHOTO FILM CO., LTD.. Invention is credited to Nii, Kazumi, Yanagi, Terukazu.
Application Number | 20050065351 10/994320 |
Document ID | / |
Family ID | 30773582 |
Filed Date | 2005-03-24 |
United States Patent
Application |
20050065351 |
Kind Code |
A1 |
Nii, Kazumi ; et
al. |
March 24, 2005 |
Luminescent device material, luminescent device using the same, and
amine compound
Abstract
A styrylamine compound comprising a structure represented by the
following formula (XI): 1 wherein Z.sup.2, R.sup.21, R.sup.22,
R.sup.26, R.sup.27 and n are as defined in the specification.
Inventors: |
Nii, Kazumi; (Kanagawa,
JP) ; Yanagi, Terukazu; (Kanagawa, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
SUITE 800
WASHINGTON
DC
20037
US
|
Assignee: |
FUJI PHOTO FILM CO., LTD.
|
Family ID: |
30773582 |
Appl. No.: |
10/994320 |
Filed: |
November 23, 2004 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10994320 |
Nov 23, 2004 |
|
|
|
10686663 |
Oct 17, 2003 |
|
|
|
10686663 |
Oct 17, 2003 |
|
|
|
09499460 |
Feb 7, 2000 |
|
|
|
6689491 |
|
|
|
|
Current U.S.
Class: |
548/110 ;
548/129; 548/132; 549/288 |
Current CPC
Class: |
C09K 2211/1044 20130101;
Y10S 428/917 20130101; C09K 2211/1037 20130101; C09K 2211/1088
20130101; H01L 51/5012 20130101; C09K 2211/1007 20130101; C09K
2211/1033 20130101; C09K 2211/1014 20130101; C09K 2211/1003
20130101; C09K 2211/14 20130101; C09K 11/06 20130101; C09K
2211/1011 20130101; C09K 2211/1092 20130101 |
Class at
Publication: |
548/110 ;
548/129; 548/132; 549/288 |
International
Class: |
C07F 007/02; C07D
271/12 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 8, 1999 |
JP |
HEI. 11-30190 |
Mar 12, 1999 |
JP |
HEI. 11-66923 |
Jul 23, 1999 |
JP |
HEI. 11-209820 |
Aug 24, 1999 |
JP |
HEI. 11-237266 |
Claims
What is claimed is:
1. A styrylamine compound comprising a structure represented by the
following formula (XI): 72wherein R.sup.21 and R.sup.22, which are
the same or different, each represent an aryl group or a
heterocyclic group; R.sup.21 and R.sup.22 may combine with each
other to form a ring; R.sup.27 represents a substituent group; n
represents an integer of 0 to 4, provided that when n is 2, 3 or 4,
the R.sup.27 groups are the same or different; R.sup.26 represents
a hydrogen atom, an alkyl group, an alkenyl group, an acyl group, a
sulfonyl group, an alkoxycarbonyl group, a carbonamido group or a
cyano group; Z.sup.2 represents a 1,3-indanedione nucleus having
one or more substituent groups which combine with each other to
complete a condensed ring or which are each an alkyl, aryl,
heterocyclic, alkenyl or silyl group, a furanone nucleus, an
oxyindole nucleus, an imidazolidone nucleus, a
dioxobenzothiophene-3-one nucleus, a coumaranone nucleus, a
1-indanone nucleus substituted at the 3-position by an alkyl, aryl
or heterocyclic group, a benzofuran-3-one nucleus, a
2-thio-2,4-thiazolidinedione nucleus, a 2-thio-2,4-oxazolidinedione
nucleus, a 2-thio-2,5-thiazolidinedione nucleus, a
2,4-thiazolidinedione nucleus, 2,4-imidazolidinedione nucleus,
2-thio-2,4-imidazolidinedione nucleus, or a 2-imidazoline-5-one
nucleus; and at least one of the oxygen atom and sulfur atom of the
carbonyl or thiocarbonyl group attached to the cyclic skeleton
constituting Z.sup.2 may be substituted with N--R.sup.2a or
CR.sup.2bR.sup.2c, wherein R.sup.2a, R.sup.2b and R.sup.2c each
represent a hydrogen atom or a substituent group.
2. The compound of claim 1, wherein R.sup.21 and R.sup.22 represent
an aryl group.
3. The compound of claim 1, wherein R.sup.21 and R.sup.22 each
represents a heterocyclic group.
4. The compound of claim 1, wherein R.sup.21 represents an aryl
group and R.sup.22 represents a heterocyclic group.
5. The compound of claim 2, wherein the aryl group is selected from
the group consisting of monocyclic and bicyclic aryl groups
containing 6 to 30 carbon atoms.
6. The compound of claim 2, wherein the aryl group is selected from
the group consisting of phenyl and naphthyl group containing 6 to
20 carbon atoms.
7. The compound of claim 3, wherein R.sup.21 and R.sup.22 are each
selected from the group consisting of 3- to 10-membered, saturated
or unsaturated heterocyclic groups containing at least one
nitrogen, oxygen or sulfur atom.
8. The compound of claim 7, wherein R.sup.21 and R.sup.22 are each
selected from the group consisting of 5- and 6-membered aromatic
heterocyclic groups.
9. The compound of claim 3, wherein R.sup.21 and R.sup.22 are each
selected from the group consisting of pyrrolidine, piperidine,
piperazine, morpholine, thiophene, furan, pyrrole, imidazole,
pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine,
indole, indazole, purine, thiazoline, thiazole, thiadiazole,
oxazoline, oxazole, oxadiazole, quinoline, isoquinoline,
phthalazine, naphthylizine, quinoxaline, quinazoline, cinnoline,
pteridine, acridine, phenanthroline, phenazine, tetrazole,
benzimidazole, benzoxazole, benzothiazole, benzotriazole and
tetraazaindene.
10. The compound of claim 9, wherein R.sup.21 and R.sup.22 are each
selected from the group consisting of thiophene, pyridine and
quinoline.
11. The compound of claim 4, wherein R.sup.21 is selected from the
group consisting of phenyl and naphthyl groups containing 6 to 20
carbon atoms and R.sup.22 is selected from the group consisting of
pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan,
pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine,
triazole, triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole, oxadiazole, quinoline,
isoquinoline, phthalazine, naphthylizine, quinoxaline, quinazoline,
cinnoline, pteridine, acridine, phenanthroline, phenazine,
tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole
and tetraazaindene.
12. The compound of claim 1, wherein R.sup.21 and R.sup.22 may
combine with each other to form a ring; R.sup.27 represents a
substituent group; n represents an integer of 0 to 4, provided that
when n is 2, 3 or 4, the R.sup.27 groups are the same or
different.
13. The compound of claim 1, wherein R.sup.26 represents a hydrogen
atom, an alkyl group or an alkenyl group.
14. The compound of claim 13, wherein R.sup.26 represents a
hydrogen atom.
15. The compound of claim 1, wherein R.sup.26 represents an acyl
group, a sulfonyl group, an alkoxycarbonyl group, a carbonamido
group or a cyano group.
16. The compound of claim 1, wherein Z.sup.2 represents a
1,3-indanedione nucleus having one or more substituent groups which
combine with each other to complete a condensed ring or which are
each an alkyl, aryl, heterocyclic, alkenyl or silyl group, a
furanone nucleus, an oxyindole nucleus, an imidazolidone nucleus, a
dioxobenzothiophene 3-one nucleus, a coumaranone nucleus, a
1-indanone nucleus substituted at the 3-position by an alkyl, aryl
or heterocyclic group, a benzofuran 3-one nucleus, a
2-thio-2,4-thiazolidinedione nucleus, a 2-thio-2,4-oxazolidinedione
nucleus, a 2-thio-2,5-thiazolidinedione nucleus, a
2,4-thiazolidinedione nucleus, a 2,4-imidazolidinedione nucleus, a
2-thio-2,4-imidazolidinedion- e nucleus or a 2-imidazoline-5-one
nucleus.
17. The compound of claim 16, wherein Z.sup.2 represents a
1,3-indanedione nucleus having one or more substituent groups, a 5
dioxobenzothiophene-3-one nucleus, a 1-indanone nucleus substituted
at the 3-position, a benzofuran 3-one nucleus or a
2-thio-2,4-thiazolidinedi- one nucleus.
18. The compound of claim 1, wherein n is 0.
Description
CROSS REFERENCE TO RELATED APPLICATION
[0001] This is a Divisional Application of pending prior
application Ser. No. 10/686,663 filed Oct. 17, 2003, which is a
divisional application of U.S. application Ser. No. 09/499,460 (now
U.S. Pat. No. 6,689,491) filed Feb. 7, 2000; the disclosures of
which are incorporated herein by reference.
FIELD OF THE INVENTION
[0002] The present invention relates to an organic luminescent
device material used for a plane light source and a plane display,
and to an organic luminescent device having high luminance. More
specifically, the invention is concerned with a luminescent
material capable of emitting a high-luminance light in the green to
red region with high efficiency under a low applied voltage and a
luminescent device using such a material. Further, the invention
relates to novel compounds capable of producing fluorescence.
BACKGROUND OF THE INVENTION
[0003] The organic luminescence devices utilizing organic
substances have favorable prospects for the use as low-priced
large-size full color display device of solid luminophor type, and
have been developed in large numbers. In general, an organic
luminescent device is constituted of a luminescent layer and a pair
of facing electrodes between which the luminescent layer is
sandwiched. The luminescence is a phenomenon that, when an electric
field is impressed between both electrodes, the negative electrode
emits electrons and the positive electrode emits positive holes and
these electrons and positive holes are injected into a luminescent
layer and recombined therein to return the energy level to the
valence electron band from the conduction band, thereby liberating
the energy as light.
[0004] Although conventional organic luminescent devices require
high driving voltage and have low luminance and low luminous
efficiency, the organic EL device comprising a lamination of thin
films containing organic compounds which luminesce with high
fluorescent quantum efficiency when a low voltage of 10 V or below
is impressed thereon has recently been proposed (Applied Physics
Letters, 51, p.913 (1987)) and much attention has been focused
thereon. More specifically, such a device produces green
luminescence of high luminance by using a metallic chelate complex
in the electron-transporting layer, a fluorescent substance in the
luminescent layer and an amine compound in a positive
hole-transporting layer. Further, when the utilization of organic
luminescent devices as full color display or light source is
intended, the devices are required to give the three primary colors
or white color from a practical point of view. Such being the case,
the devices doped with fluorescent dyes to emit light of a desired
color were reported (Journal of Applied Physics, vol. 65, p. 3610
(1989)). The technique adopted therein is effective particularly in
the case of red luminescence where the density quenching is so
serious that it is difficult to form a luminous layer with a
fluorescent dye alone, and satisfactory color purity and high
luminance are achieved thereby. However, it bears a problem such
that, in producing the device doped with a dye by the use of an
evaporation technique, a host material and a slight amount of
fluorescent dye are co-evaporated; as a result, the operation is
complicated and the devices produced tend to be uneven in
performance. From the viewpoint of simplifying the production
process and ensuring even performance for the products, therefore,
it has been desired to develop luminescent materials having
satisfactory color purity and enabling the formation of a
luminescent layer with a dye alone, especially a red luminescent
material which can achieve satisfactory chromaticity and high
luminance even when it form a luminescent layer by itself.
[0005] On the other hand, although the organic luminescent devices
which are successful in achieving high-luminance luminescence are
devices comprising organic substances laminated by vacuum
evaporation, the production of devices in accordance with a coating
method is advantageous from the viewpoints of simplicity of the
production process, processability and easiness of size expansion.
However, the devices produced by conventional coating methods are
inferior to the devices produced by evaporation methods in
luminance and luminous efficiency, and so the big problem which
confronts them is to achieve highly efficient luminescence having
high luminance. Further, the device comprising a coating of the
organic low molecular compound dispersed in an organic polymer
medium has a problem that, when the device is made to luminesce for
a long time, the planar luminescence of even quality becomes hard
to obtain due to aggregation of the organic low molecular weight
compound.
[0006] In recent years, various substances having fluorescence have
also been used for filter dyes, color conversion filters, dyes for
a photographic material, sensitizing dyes, pulp coloring dyes,
laser dyes, fluorescent drugs for medical diagnosis and organic
luminescent device materials, and the demands therefor have been
growing. However, there are known only few red fluorescent dyes
having strong fluorescence intensity and high color purity, and so
the development of new materials has been desired.
SUMMARY OF THE INVENTION
[0007] A first object of the invention is to provide a luminescent
device material and a luminescent device which can give off red
luminescence of high color purity.
[0008] A second object of the invention is to provide a luminescent
device material and a luminescent device which can give off
high-luminance, even-quality, planar luminescence in the green to
red region with high efficiency when it is driven at a low voltage,
and further ensure steady performance upon repeated use.
[0009] A third object of the invention is to provide a device
capable of ensuring consistent performance in every product thereof
and a material which enables the production of such a device and
the luminescence in the green to red region.
[0010] A fourth object of the invention is to provide a luminescent
device material which enables the device to luminesce with high
luminance and high efficiency even when it is produced by a coating
method and a luminescent device using such a material.
[0011] A fifth object of the invention is to provide a compound
capable of giving off fluorescence of high intensity in the green
to red region.
[0012] A sixth object of the invention is to provide a luminescent
device having a high thermal durability.
[0013] [1] A luminescent device material, comprising a compound
represented by the following formula (I): 2
[0014] wherein R.sup.1, R.sup.2 and R.sup.3, which are the same or
different, each represents an unsubstituted or substituted aryl
group, an unsubstituted or substituted heterocyclic group or an
unsubstituted or substituted aliphatic hydrocarbon group, provided
that at least two among R.sup.1, R.sup.2 and R.sup.3 are each an
unsubstituted or substituted aryl or heterocyclic group; any two
among R.sup.1, R.sup.2 and R.sup.3 may combine with each other to
complete a ring; provided that at least one among R.sup.1, R.sup.2
and R.sup.3 has a moiety represented by the following formula (II),
3
[0015] wherein R.sup.4, R.sup.5 and R.sup.6 each represents a
hydrogen atom or a substituent group, Z.sup.1 represents atoms (an
atomic group) forming a 5, 6 or 7-membered ring, and m represents
0, 1 or 2.
[0016] [2] A luminescent device material according to Embodiment
[1], wherein the compound of formula (I) is a compound represented
by the following formula (III): 4
[0017] wherein R.sup.1 and R.sup.2, which are the same or
different, each represents an aryl group, a heterocyclic group or
an aliphatic hydrocarbon group, provided that at least either of
them is an aryl group or a heterocyclic group, or R.sup.1 and
R.sup.2 combine with each other to complete a ring; R.sup.7
represents a substituent group and n represents an integer of 0 to
4, wherein when n is 2, 3 or 4 the R.sup.7 groups are the same or
different; R.sup.4, R.sup.5 and R.sup.6 each represent a hydrogen
atom or a substituent group; Z.sup.11 represents atoms forming a 5,
6 or 7-membered ring; and m represents 0, 1 or 2.
[0018] [3] A luminescent device material according to Embodiment
[2], wherein the compound of formula (III) is a compound
represented by the following formula (IV): 5
[0019] wherein R.sup.1 and R.sup.2, which are the same or
different, each represents an aryl group, a heterocyclic group or
an aliphatic hydrocarbon group, provided that at least either of
them is an aryl group or a heterocyclic group, or R.sup.1 and
R.sup.2 combine with each other to complete a ring; R.sup.7
represents a substituent group and n represents an integer of 0 to
4, wherein when n is 2, 3 or 4 the R.sup.7 groups are the same or
different; R.sup.4, R.sup.5 and R.sup.6 each represent a hydrogen
atom or a substituent group; X.sub.A1 represents an oxygen atom, a
sulfur atom, N-R.sub.A1 or CR.sub.A2R.sub.A3; R.sub.A1, R.sub.A2
and R.sub.A3 each represent a hydrogen atom or a substituent group;
Z.sub.A1 represents atoms forming a 5, 6 or 7-membered ring; and m
represents 0, 1 or 2.
[0020] [4] A luminescent device material according to Embodiment 3,
wherein the compound of formula (IV) is a compound represented by
the following formula (V): 6
[0021] wherein R.sup.1 and R.sup.2, which are the same or
different, each represents an aryl group, a heterocyclic group or
an aliphatic hydrocarbon group, provided that at least either of
them is an aryl group or a heterocyclic group, or R.sup.1 and
R.sup.2 combine with each other to complete a ring; R.sup.7
represents a substituent group and n represents an integer of 0 to
4, wherein when n is 2, 3 or 4 the R.sup.7 groups are the same or
different; R.sup.4, R.sup.5 and R.sup.6 each represent a hydrogen
atom or a substituent group; X.sub.B1 and X.sub.B2 each represent
an oxygen atom, a sulfur atom, N-R.sub.B1 or CR.sub.B2R.sub.B3;
R.sub.B1, R.sub.B2 and R.sub.B.sup.3 each represent a hydrogen atom
or a substituent group; Z.sub.B1 represents atoms forming a 5, 6 or
7-membered ring, provided that the 5-membered ring formed by
Z.sub.B1 is a substituted 1,3-indanedione nucleus, a heterocyclic
ring-condensed cyclopenta-1,3-dione nucleus or a
3,5-pyrazolidinedione nucleus; and m represents 0, 1 or 2.
[0022] [5] A luminescent device material according to Embodiment
[3], wherein the compound of formula (IV) is a compound represented
by the following formula (VI): 7
[0023] wherein R.sup.1 and R.sup.2, which are the same or
different, each represents an aryl group, a heterocyclic group or
an aliphatic hydrocarbon group, provided that at least either of
them is an aryl group or a heterocyclic group, or R.sup.1 and
R.sup.2 combine with each other to complete a ring; R.sup.7
represents a substituent group and n represents an integer of 0 to
4, wherein when n is 2, 3 or 4 the R.sup.7 groups are the same or
different; R.sup.4, R.sup.5 and R.sup.6 each represent a hydrogen
atom or a substituent group; X.sub.C represents an oxygen atom, a
sulfur atom, N--R.sub.C1 or CR.sub.C2R.sub.C3; R.sub.C1, R.sub.C2
and R.sub.C3 each represent a hydrogen atom or a substituent group;
Y.sub.C1 and Y.sub.C2 each represent a nitrogen atom or
C--R.sub.C4; R.sub.C4 represents a hydrogen atom or a substituent
group; Z.sub.C1 represents atoms completing a 5, 6 or 7-membered
ring, provided that the 5-membered ring completed by Z.sub.C1 is an
isooxazolinone nucleus, an oxazolinone nucleus, a furanone nucleus,
an oxyindole nucleus or an imidazolidone nucleus; and m represents
0, 1 or 2.
[0024] [6] A luminescent device material according to Embodiment
[3], wherein the compound of formula (IV) is a compound represented
by the following formula (VII): 8
[0025] wherein R.sup.1 and R.sup.2, which are the same or
different, each represents an aryl group, a heterocyclic group or
an aliphatic hydrocarbon group, provided that at least either of
them is an aryl group or a heterocyclic group; R.sup.1 and R.sup.2
may combine with each other to complete a ring; R.sup.7 represents
a substituent group and n represents an integer of 0 to 4, wherein
when n is 2, 3 or 4 the R.sup.7 groups are the same or different;
R.sup.4, R.sup.5 and R.sup.6 each represent a hydrogen atom or a
substituent group; X.sub.D represents an oxygen atom, a sulfur
atom, N--R.sub.D1 or CR.sub.D2R.sub.D3; R.sub.D1, R.sub.D2 and
R.sub.D3 each represent a hydrogen atom or a substituent group;
Z.sub.D1 represents atoms completing a 5, 6 or 7-membered ring; m
represents 0, 1 or 2: and R.sub.D represents a substituent group
and d represents an integer of 0 to 4, wherein when d is 2, 3 or 4
the R.sub.D groups are the same or different.
[0026] [7] A luminescent device material according to Embodiment
[3], wherein the compound of formula (IV) is a compound represented
by the following formula (VIII): 9
[0027] wherein R.sup.1 and R.sup.2, which are the same or
different, each represents an aryl group, a heterocyclic group or
an aliphatic hydrocarbon group, provided that at least either of
them is an aryl group or a heterocyclic group; R.sup.1 and R.sup.2
may combine with each other to complete a ring; R.sup.7 represents
a substituent group and n represents an integer of 0 to 4, wherein
when n is 2, 3 or 4 the R.sup.7 groups are the same or different;
R.sup.4, R.sup.5 and R.sup.6 each represent a hydrogen atom or a
substituent group; X.sub.E represents an oxygen atom, a sulfur
atom, N--R.sub.E1 or CR.sub.E2R.sub.E3; R.sub.E1, R.sub.E2 and
R.sub.E3 each represent a hydrogen atom or a substituent group;
Y.sub.E1 and Y.sub.E2 each represent a nitrogen atom or
C--R.sub.E4; R.sub.E.sup.4 represents a hydrogen atom or a
substituent group; Z.sub.E1 represents atoms completing a 5, 6 or
7-membered ring; and m represents 0, 1 or 2.
[0028] [8] A luminescent device material according to Embodiment
[3], wherein the compound of formula (IV) is a compound represented
by the following formula (IX): 10
[0029] wherein R.sup.1 and R.sup.2, which are the same or
different, each represents an aryl group, a heterocyclic group or
an aliphatic hydrocarbon group, provided that at least either of
them is an aryl group or a heterocyclic group, R.sup.1 and R.sup.2
may combine with each other to complete a ring; R.sup.7 represents
a substituent group and n represents an integer of 0 to 4, wherein
when n is 2, 3 or 4 the R.sup.7 groups are the same or different;
R.sup.4, R.sup.5 and R.sup.6 each represent a hydrogen atom or a
substituent group; X.sub.F1 and X.sub.F2 each represents an oxygen
atom, a sulfur atom, N--R.sub.F1 or CR.sub.F2R.sub.F3; R.sub.F1,
R.sub.F2 and R.sub.F3 each represent a hydrogen atom or a
substituent group; Y.sub.F1 and Y.sub.F2 each represent an oxygen
atom, a sulfur atom or N--R.sub.F5; R.sub.F.sup.5 represents a
hydrogen atom or a substituent group; and m represents 0, 1 or
2.
[0030] [9] A luminescent device material according to Embodiment
[3], wherein the compound of formula (IV) is a compound represented
by the following formula (X): 11
[0031] wherein R.sup.1 and R.sup.2, which are the same or
different, each represents an aryl group, a heterocyclic group or
an aliphatic hydrocarbon group, provided that at least either of
them is an aryl group or a heterocyclic group, or R.sup.1 and
R.sup.2 combine with each other to complete a ring; R.sup.7
represents a substituent group and n represents an integer of 0 to
4, wherein when n is 2, 3 or 4 the R.sup.7 groups are the same or
different; R.sup.4, R.sup.5 and R.sup.6 each represent a hydrogen
atom or a substituent group; X.sub.G represents an oxygen atom, a
sulfur atom, N--R.sub.G1 or CR.sub.G2R.sub.G3; R.sub.G1, R.sub.G2
and R.sub.G3 each represent a hydrogen atom or a substituent group;
Y.sub.G1 and Y.sub.G2 each represent a nitrogen atom or
C--R.sub.G4; R.sub.G4 represents a hydrogen atom or a substituent
group; m.sub.1 represents 1 or 2; Z.sub.G1 represents atoms
completing a 5, 6 or 7-membered ring; and m represents 0, 1 or
2.
[0032] [10] A styrylamine compound having a structure represented
by the following formula (XI): 12
[0033] wherein R.sup.21 and R.sup.22, which are the same or
different, each represent an aryl group or a heterocyclic group,
R.sup.21 and R.sup.22 may combine with each other to form a ring;
R.sup.27 represents a substituent group and n represents an integer
of 0 to 4, wherein when n is 2, 3 or 4 the R.sup.27 groups are the
same or different; R.sup.26 represents a hydrogen atom, an alkyl
group, an alkenyl group, an acyl group, a sulfonyl group, an
alkoxycarbonyl group, a carbonamido group or a cyano group; and
Z.sup.2 represents a 1,3-indanedione nucleus having substituent
groups which combine with each other to complete a condensed ring
or which are each an alkyl, aryl, heterocyclic, alkenyl or silyl
group, a furanone nucleus, an oxyindole nucleus, an imidazolidone
nucleus, a dioxobenzothiophene-3-one nucleus, a coumaranone
nucleus, a 1-indanone nucleus substituted at the 3-position by an
alkyl, aryl or heterocyclic group, a benzofuran-3-one nucleus, a
2-thio-2,4-thiazolidine- dione nucleus, a
2-thio-2,4-oxazolidinedione nucleus, a 2-thio-2,5-thiazolidinedione
nucleus, a 2,4-thiazolidinedione nucleus, 2,4-imidazolidinedione
nucleus, 2-thio-2,4-imidazolidinedione nucleus, a
2-imidazoline-5-one nucleus or a nucleus formed by replacing the
carbonyl oxygen or the thiocarbonyl sulfur attached to the cyclic
skeleton constituting Z.sup.2 with N--R.sup.2a or
CR.sup.2bR.sup.2c, wherein R.sup.2a, R.sup.2b and R.sup.2c each
represent a hydrogen atom or a substituent group.
[0034] [11] A luminescent device material according to Embodiment
[1], wherein the compound of formula (I) is a compound represented
by the following formula (XII): 13
[0035] wherein Ar.sup.31 represents an arylene group or a divalent
heterocyclic group; R.sup.32 represents an aryl group, a
heterocyclic group or an aliphatic hydrocarbon group; R.sup.34,
R.sup.35 and R.sup.36 each represent a hydrogen atom or a
substitutent group; Z.sup.3 represents atoms forming a 5, 6 or
7-membered ring; m represents 0, 1 or 2; t is an integer of at
least 2, and one combination made with Ar.sup.31, R.sup.32,
R.sup.34, R.sup.35, R.sup.36, Z.sup.3 and m is the same as or
different from another combination made therewith; and L represents
a t-valent linkage group.
[0036] [12] A luminescent device material according to Embodiment
[1], wherein the compound of formula (I) is a compound represented
by the following formula (XIII): 14
[0037] wherein Ar.sup.41 represents an arylene group or a divalent
heterocyclic group; R.sup.42 represents an aryl group, a
heterocyclic group or an aliphatic hydrocarbon group; R.sup.44,
R.sup.45 and R.sup.46 each represent a hydrogen atom or a
substitutent group; Z.sup.4 represents atoms forming a 5, 6 or
7-membered ring; m represents 0, 1 or 2; p represents 2 or 3, and
two or three combinations made with Ar.sup.41, R.sup.42, R.sup.44,
R.sup.45, R.sup.45, Z.sup.4 and m are the same or different.
[0038] [13] A luminescent device material according to Embodiment
[11], wherein the compound of formula (XII) is a compound
represented by the following formula (XIV): 15
[0039] wherein R.sup.54, R.sup.55 and R.sup.56 each represent a
hydrogen atom or a substituent group; R.sup.57 and R.sup.58 each
represent a substituent group; q represents an integer of 0 to 4,
and when q is 2, 3 or 4 the R.sup.57 groups are the same or
different; r represents an integer of 0 to 5, and when r is 2, 3, 4
or 5 the R.sup.58 groups are the same or different; Z.sup.5
represents atoms forming a 5, 6 or 7-membered ring; m represents 0,
1 or 2; t represents an integer of at least 2, and one combination
made with R.sup.54, R.sup.55, R.sup.56, R.sup.57, R.sup.58,
Z.sup.5, m, q and r is the same as or different from another
combination made therewith; and L represents a t-valent linkage
group.
[0040] [14] A luminescent device material according to Embodiment
[12], wherein the compound of formula (XIII) is a compound
represented by the following formula (XV): 16
[0041] wherein R.sup.62 represents an aryl group, a heterocyclic
group or an aliphatic hydrocarbon group; R.sup.64, R.sup.65 and
R.sup.66 each represent a hydrogen atom or a substituent group;
R.sup.67 represents a substituent group; q represents an integer of
0 to 4, and when q is 2, 3 or 4 the R.sup.67 groups are the same or
different; Z.sup.6 represents atoms forming a 5, 6 or 7-membered
ring; m represents 0, 1 or 2; p represents 2 or 3, and two or three
combinations made with R.sup.62, R.sup.64, R.sup.65, R.sup.66,
R.sup.67, Z.sup.6, m and q are the same or different.
[0042] [15] A luminescent device material according to claim 13,
wherein the compound of formula (XIV) is a compound represented by
the following formula (XVI): 17
[0043] wherein R.sup.74 represents a hydrogen atom or a substituent
group; R.sup.77 and R.sup.78 each represent a substituent group; q
represents an integer of 0 to 4, and when q is 2, 3 or 4 the
R.sup.77 groups are the same or different; r represents an integer
of 0 to 5, and when r is 2, 3, 4 or 5 the R.sup.78 groups are the
same or different; Z.sup.7 represents atoms forming a 5, 6 or
7-membered ring; t represents an integer of at least 2, and one
combination made with R.sup.74, R.sup.77, R.sup.78, Z.sup.7, q and
r is the same as or different from another combination made
therewith; and L represents a t-valent linkage group.
[0044] [16] A luminescent device material according to Embodiment
[15], wherein the compound of formula (XVI) is a compound
represented by the following formula (XVII): 18
[0045] wherein R.sup.84 represents a hydrogen atom or a substituent
group; R.sup.87 and R.sup.88 each represent a substituent group; q
represents an integer of 0 to 4, and when q is 2, 3 or 4 the
R.sup.87 groups are the same or different; r represents an integer
of 0 to 5, and when r is 2, 3, 4 or 5 the R.sup.88 groups are the
same or different; Z.sup.8 represents atoms forming a 5, 6 or
7-membered ring; X.sup.8 represents an oxygen atom, a sulfur atom,
N--R.sup.A1 or CR.sup.A2R.sup.A3; R.sup.A1, R.sup.A2 and R.sup.A3
each represent a hydrogen atom or a substituent group; t represents
an integer of at least 2, and one combination made with R.sup.84,
R.sup.87, R.sup.88, Z.sup.8, X.sup.8, q and r is the same as or
different from another combination made therewith; and L represents
a t-valent linkage group.
[0046] [17] A styrylamine compound having a structure represented
by the following formula (XVIII): 19
[0047] wherein R.sup.94 represents a hydrogen atom or a substituent
group; R.sup.97 and R.sup.98 each represent a substituent group; q
represents an integer of 0 to 4, and when q is 2, 3 or 4 the
R.sup.97 groups are the same or different; r represents an integer
of 0 to 5, and when r is 2, 3, 4 or 5 the R.sup.98 groups are the
same or different; Z.sup.9 represents atoms forming a 5, 6 or
7-membered ring; X.sup.9 represents an oxygen atom, a sulfur atom,
N--R.sup.A1 or CR.sup.A2R.sup.A3; R.sup.A1, R.sup.A2 and R.sup.A3
each represent a hydrogen atom or a substituent group; t represents
an integer of at least 2, and one combination made with R.sup.94,
R.sup.97, R.sup.98, Z.sup.9, X.sup.9, q and r is the same as or
different from another combination made therewith; and L represents
a t-valent linkage group.
[0048] [18] A luminescent device having at least one layer of an
organic thin film between electrodes, with the device comprising at
least one of the compounds represented by formulae (I) and (III) to
(XVIII) as defined in Embodiments [1] to [17] respectively.
[0049] [19] A luminescent device having at least one layer of an
organic thin film between electrodes, with the device comprising at
least one layer wherein at least one of the compounds represented
by formulae (I) and (III) to (XVIII) as defined in claims 1 to 17
respectively is dispersed in a polymer.
DETAILED DESCRIPTION OF THE INVENTION
[0050] Firstly, the compound represented by the foregoing formula
(I) is described below in detail.
[0051] R.sup.1, R.sup.2 and R.sup.3 in formula (I) may be the same
or different. And each of them represents an aryl group, a
heterocyclic group or an aliphatic hydrocarbon group, provided that
at least two of them are each an aryl group or a heterocyclic
group.
[0052] Suitable examples of an aryl group represented by R.sup.1,
R.sup.2 and R.sup.3 each include monocyclic and bicyclic aryl
groups containing 6 to 30 carbon atoms (such as phenyl and naphthyl
groups), preferably phenyl and naphthyl groups containing 6 to 20
carbon atoms, particularly preferably phenyl and naphthyl groups
containing 6 to 14 carbon atoms.
[0053] The heterocyclic group represented by R.sup.1, R.sup.2 and
R.sup.3 each is a 3- to 10-membered, saturated or unsaturated
heterocyclic group containing at least one nitrogen, oxygen or
sulfur atom. Such a heterocyclic ring may be a single ring, or a
condensed ring formed by fusing together with another ring.
[0054] Suitable examples of a heterocyclic group include 5- to
6-membered aromatic heterocyclic groups, preferably nitrogen,
oxygen or/and sulfur-containing 5- to 6-membered aromatic
heterocyclic groups, particularly preferably 5- to 6-membered
aromatic heterocyclic groups containing one to two nitrogen atoms
or/and one to two sulfur atoms. Examples of such a heterocyclic
ring include pyrrolidine, piperidine, piperazine, morpholine,
thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine,
pyridazine, triazole, triazine, indole, indazole, purine,
thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole,
quinoline, isoquinoline, phthalazine, naphthylizine, quinoxaline,
quinazoline, cinnoline, pteridine, acridine, phenanthroline,
phenazine, tetrazole, benzimidazole, benzoxazole, benzothiazole,
benzotriazole and tetraazaindene. Of these heterocyclic rings,
thiophene, pyridine and quinoline are preferred over the
others.
[0055] The aliphatic hydrocarbon groups represented by R.sup.1,
R.sup.2 and R.sup.3 each include straight-chain, branched or cyclic
alkyl groups (containing preferably 1 to 20 carbon atoms, more
preferably 1 to 12 carbon atoms, particularly preferably 1 to 8
carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, n-octyl,
n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl and cyclohexyl),
alkenyl groups (containing preferably 2 to 20 carbon atoms, more
preferably 2 to 12 carbon atoms, particularly preferably 2 to 8
carbon atoms, such as vinyl, allyl, 2-butenyl and 3-pentenyl) and
alkynyl groups (containing preferably 2 to 20 carbon atoms, more
preferably 2 to 12 carbon atoms, particularly preferably 2 to 8
carbon atoms, such as propargyl and 3-pentynyl). Of these groups,
alkyl groups are preferred over the others.
[0056] The aryl, heterocyclic, or aliphatic hydrocarbon group
represented by R.sup.1, R.sup.2 and R.sup.3 each may have a
substituent group. Examples of such a substituent group include
alkyl groups (containing preferably 1 to 20 carbon atoms, more
preferably 1 to 12 carbon atoms, particularly preferably 1 to 8
carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl,
n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl and
cyclohexyl), alkenyl groups (containing preferably 2 to 20 carbon
atoms, more preferably 2 to 12 carbon atoms, particularly
preferably 2 to 8 carbon atoms, such as vinyl, allyl, 2-butenyl and
3-pentenyl), alkynyl groups (containing preferably 2 to 20 carbon
atoms, more preferably 2 to 12 carbon atoms, particularly
preferably 2 to 8 carbon atoms, such as propargyl and 3-pentynyl),
aryl groups (containing preferably 6 to 30 carbon atoms, more
preferably 6 to 20 carbon atoms, particularly preferably 6 to 12
carbon atoms, such as phenyl, p-methylphenyl and naphthyl), amino
groups (including an unsubstituted amino group and amino groups
substituted, e.g., by alkyl, alkenyl, aralkyl, aryl or/and
heterocyclic groups, and each containing preferably 0 to 20 carbon
atoms, more preferably 0 to 10 carbon atoms, particularly
preferably 0 to 6 carbon atoms, such as amino, methylamino,
dimethylamino, diethylamino, dibenzylamino and phenylamino), alkoxy
groups (containing preferably 1 to 20 carbon atoms, more preferably
1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms,
such as methoxy, ethoxy and butoxy), aryloxy groups (containing
preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon
atoms, particularly preferably 6 to 12 carbon atoms, such as
phenoxy and 2-naphthyloxy), acyl groups (containing preferably 1 to
20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly
preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl
and pivaroyl), alkoxycarbonyl groups (containing preferably 2 to 20
carbon atoms, more preferably 2 to 16 carbon atoms, particularly
preferably 2 to 12 carbon atoms, such as methoxycarbonyl and
ethoxycarbonyl), aryloxycarbonyl groups (containing preferably 7 to
20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly
preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl),
acyloxy groups (containing preferably 2 to 20 carbon atoms, more
preferably 2 to 16 carbon atoms, particularly preferably 2 to 10
carbon atoms, such as acetoxy and benzoyloxy), acylamino groups
(containing preferably 2 to 20 carbon atoms, more preferably 2 to
16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such
as acetylamino and benzoylamino), alkoxycarbonylamino groups
(containing preferably 2 to 20 carbon atoms, more preferably 2 to
16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such
as methoxycarbonylamino), aryloxycarbonylamino groups (containing
preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon
atoms, particularly preferably 7 to 12 carbon atoms, such as
phenyloxycarbonylamino), sulfonylamino groups (containing
preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon
atoms, particularly preferably 1 to 12 carbon atoms, such as
methanesulfonylamino and benzenesulfonylamino), sulfamoyl groups
(containing preferably 0 to 20 carbon atoms, more preferably 0 to
16 carbon atoms, particularly preferably 0 to 12 carbon atoms, such
as sulfamoyl, methylsulfamoyl, dimethylsulfamoyl and
phenylsulfamoyl), carbamoyl groups (containing preferably 1 to 20
carbon atoms, more preferably 1 to 16 carbon atoms, particularly
preferably 1 to 12 carbon atoms, such as carbamoyl,
methylcarbamoyl, diethylcarbamoyl and phenylcarbamoyl), alkylthio
groups (containing preferably 1 to 20 carbon atoms, more preferably
1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
such as methylthio and ethylthio), arythio groups (containing
preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon
atoms, particularly preferably 6 to 12 carbon atoms, such as
phenylthio), sulfonyl groups (containing preferably 1 to 20 carbon
atoms, more preferably 1 to 16 carbon atoms, particularly
preferably 1 to 12 carbon atoms, such as mesyl and tosyl), sulfinyl
groups (containing preferably 1 to 20 carbon atoms, more preferably
1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
such as methanesulfinyl and benzenesulfinyl), ureido groups
(containing preferably 1 to 20 carbon atoms, more preferably 1 to
16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such
as ureido, methylureido and phenylureido) phosphoric acid amido
groups (containing preferably 1 to 20 carbon atoms, more preferably
1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms,
such as diethylphosphoric acid amido and phenylphosphoric acid
amido), a hydroxyl group, a mercapto group, halogen atoms (such as
fluorine, chlorine, bromine and iodine atoms), a cyano group, a
sulfo group, a carboxyl group, a nitro group, a hydroxamic acid
group, a sulfino group, a hydrazino group, an imino group,
heterocyclic groups (containing preferably 1 to 20 carbon atoms,
more preferably 1 to 12 carbon atoms, and further containing
nitrogen, oxygen or/and sulfur atoms as hetero atom(s), such as
groups derived from pyrrolidine, piperidine, piperazine,
morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
pyridine, pyrazine, pyridazine, triazole, triazine, indole,
indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline,
oxazole, oxadiazole, quinoline, isoquinoline, phthalazine,
naphthylizine, quinoxaline, quinazoline, cinnoline, pteridine,
acridine, phenanthroline, phenazine, tetrazole, benzimidazole,
benzoxazole, benzothiazole, benzotriazole and tetraazaindene) and
silyl groups (containing preferably 3 to 40 carbon atoms, more
preferably 3 to 30 carbon atoms, particularly preferably 3 to 24
carbon atoms, such as trimethylsilyl and triphenylsilyl) These
substituent groups each may further be substituted. When two or
more substituent groups are present, they may be the same or
different and, if possible, may form a ring by combining with each
other.
[0057] Of the substituent groups recited above, alkyl, alkenyl,
aralkyl, aryl, alkoxy, amino, acyl, alkoxycarbonyl,
aryloxycarbonyl, carbonylamino, sulfonylamino, sulfamoyl,
carbamoyl, hydroxyl, silyl and heterocyclic groups are preferred
over the other. Among these groups, alkyl, alkenyl, aralkyl, aryl,
alkoxy, amino, carbonylamino, sulfonylamino, silyl and heterocyclic
groups are more favorable. In particular, alkyl, alkenyl, aryl,
alkoxy, substituted amino and silyl groups are advantageous over
the others.
[0058] The term "substituted amino group" as used herein refers to
the group represented by --NR.sub.a(R.sub.b), wherein R.sub.a and
R.sub.b may be the same or different and they each represent an
alkyl group, an alkenyl group, an aralkyl group, an aryl group or a
heterocyclic group.
[0059] Moreover, at least one among the groups R.sup.1, R.sup.2 and
R.sup.3 contains a moiety represented by the following formula
(II).
[0060] The expression "contains a moiety represented by formula
(II)" as used herein means that the substituent group of an aryl,
heterocyclic or aliphatic hydrocarbon group represented by R.sup.1,
R.sup.2 and R.sup.3 each may be the moiety of formula (II) or may
further be substituted by the moiety of formula (II).
[0061] The formula (II) is as follows: 20
[0062] wherein R.sup.4, R.sup.5 and R.sup.6 each represent a
hydrogen atom or a substituent group, Z.sup.1 represents atoms
forming a 5, 6 or 7-membered ring, and m represents 0, 1 or 2.
[0063] Further, any two among R.sup.4, R.sup.5 and R.sup.6 may
combine with each other to complete a ring, or each of them may
combine with R.sup.1, R.sup.2 or R.sup.3 to complete a ring.
Examples of a substituent group represented by R.sup.4, R.sup.5 and
R.sup.6 each include the groups recited above as substituent groups
which the aryl, heterocyclic or aliphatic hydrocarbon group
represented by R.sup.1, R.sup.2 and R.sup.3 each may have. It is
desirable for m to be 0 or 1, particularly 0.
[0064] Z.sup.1 represents atoms forming a 5, 6 or 7-membered ring,
which may have another ring in a fused state. Suitable examples of
a ring formed by Z.sup.1 include rings employed as acidic nuclei in
conventional merocyanine dyes.
[0065] The ring preferred as acidic nucleus represented by Z.sup.1
is a ring represented by the following formula (A): 21
[0066] wherein X.sup.A represents an oxygen atom, a sulfur atom,
N--R.sup.A1 or CR.sup.A2R.sup.A3, R.sup.A1, R.sup.A2 and R.sup.A3
each represent a hydrogen atom or a substituent group, and Z.sup.A
represents atoms completing a 5, 6 or 7-membered ring, preferably
constituted of any of carbon, nitrogen, oxygen and sulfur
atoms.
[0067] The 5, 6 or 7-membered ring completed by Z.sup.A may further
form a condensed ring.
[0068] To be concrete, R.sup.A1 represents a hydrogen atom, an
aliphatic hydrocarbon group, an aryl group or a heterocyclic
group.
[0069] The aliphatic hydrocarbon group represented by R.sup.A1 is a
straight-chain, branched or cyclic alkyl group (containing
preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon
atoms, particularly preferably 1 to 12 carbon atoms, such as
methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl,
n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl), an alkenyl
group (containing preferably 2 to 30 carbon atoms, more preferably
2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms,
such as vinyl, allyl, 2-butenyl or 3-pentenyl) or an alkynyl group
(containing preferably 2 to 30 carbon atoms, more preferably 2 to
20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such
as propargyl or 3-pentynyl), preferably an alkyl group or an
alkenyl group, particularly preferably a methyl group, an ethyl
group, a propyl group, a butyl group or an allyl group.
[0070] The aryl group suitable for R.sup.A1 is a monocyclic
orbicyclic aryl group containing 6 ro 30 carbon atoms (e.g., phenyl
or naphthyl), preferably a phenyl group containing 6 to 20 carbon
atoms, particularly preferably a phenyl group containing 6 to 12
carbon atoms.
[0071] The heterocyclic group represented by R.sup.A1 is a group
derived from a 3- to 10-membered saturated or unsaturated
heterocyclic ring containing at least one nigrogen, oxygen or
sulfur atom. Such a ring may be a single ring or a condensed ring
formed by fusion with another ring.
[0072] The heterocyclic group suitable for R.sup.A1 is a 5 or
6-membered aromatic heterocyclic group, preferably a 5 or
6-membered nitrogen-containing aromatic heterocyclic group,
particularly preferably a 5 or 6-membered aromatic heterocyclic
group containing one or two nitrogen atoms. Examples of such a
heterocyclic ring include pyrrolidine, piperidine, piperazine,
morpholine, thiophene, furan, pyrrole, imidazole, pyrazole,
pyridine, pyrazine, pyridazine, triazole, triazine, indole,
indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline,
oxazole, oxadiazole, quinoline, isoquinoline, phthalazine,
naphthylizine, quinoxaline, quinazoline, cinnoline, pteridine,
acridine, phenanthroline, phenazine, tetrazole, benzimidazole,
benzoxazole, benzothiazole, benzotriazole and tetraazaindene. Of
these rings, pyrrole, imidazole, pyrazole, pyridine, pyrazine,
pyridazine, triazole, triazine, indole, indazole, thiadiazole,
oxadiazole, quinoline, phthalazine, quinoxaline, quinazoline,
cinnoline, tetrazole, thiazole, oxazole, benzimidazole,
benzoxazole, benzothiazole and benzotriazole are preferred over the
others. In particular, pyridine and quinoline are advantageous over
the others.
[0073] The aliphatic hydrocarbon group, the aryl group and the
heterocyclic group represented by R.sup.A1 may have a substituent
group, and examples of such a substituent group include those
recited above as the substituent groups which R.sup.1, R.sup.2 and
R.sup.3 can have.
[0074] The group preferred as R.sup.A1 is an alkyl group, an
alkenyl group or an aryl group, especially an alkyl group or a
phenyl group.
[0075] The substituent group represented by R.sup.A2 and R.sup.A3
each include those recited above as the substituent groups which
R.sup.1, R.sup.2 and R.sup.3 each can have.
[0076] R.sup.A2 and R.sup.A3 each preferably represent a hydrogen
atom, a cyano group, an oxycarbonyl group, an acyl group, a
sulfonyl group, a thioether group, a carbamoyl group or a sulfamoyl
group. Therein, however, the case of R.sup.A2=R.sup.A3=hydrogen
atom is not included.
[0077] The oxycarbonyl group, the acyl group, the sulfonyl group
and the thioether group which R.sup.A2 and R.sup.A3 each can
represent are respectively oxycarbonyl, acyl, sulfonyl and
thioether groups substituted by an aliphatic hydrocarbon, aryl or
heterocyclic group. This aliphatic hydrocarbon, aryl or
heterocyclic moiety of such groups each has the same meaning as the
aliphatic hydrocarbon, aryl or heterocyclic group respectively
which is illustrated above as a group represented by R.sup.A1.
[0078] The carbamoyl group and the sulfamoyl group which R.sup.A2
and R.sup.A3 each can represent are unsubstituted or aliphatic
hydrocarbon, aryl or heterocyclic group-substituted carbamoyl and
sulfamoyl groups respectively. This substituted moiety of such
groups each, namely an aliphatic hydrocarbon, aryl or heterocyclic
group, has the same meaning as the aliphatic hydrocarbon, aryl or
heterocyclic group respectively which is illustrated above as a
group represented by R.sup.A1.
[0079] Of the acidic nuclei represented by the foregoing formula
(A), the nuclei represented by the following formula (B), (C), (D),
(E), (F) or (G) are employed to advantage. 22
[0080] wherein X.sup.B1 and X.sup.B2 each represent an oxygen atom,
a sulfur atom, N--R.sup.B1 or CR.sup.B2R.sup.B3, R.sup.B1, R.sup.B2
and R.sup.B3 each represent a hydrogen atom or a substituent group,
and Z.sup.B represents atoms completing a 5, 6 or 7-membered ring,
preferably constituted of any of carbon, nitrogen, oxygen and
sulfur atoms. The 5- to 7-membered ring completed by Z.sup.B may
further form a condensed ring. R.sup.B1, R.sup.B2 and R.sup.B3 have
the same meanings as R.sup.A1, R.sup.A2 and R.sup.A3 respectively.
Examples of an acidic nucleus represented by formula (B) include
1,3-indanedione nuclei, heterocyclic ring-condensed
cyclopenta-1,3-dione nuclei, 3,5-pyrazolinedione nuclei,
1,3-cyclohexanedione nuclei, 1,3-dioxane-4,6-dione nuclei and
2,4,6-triketohexahydropyrimidine nuclei (including barbituric or
2-thiobarbituric acid and derivatives thereof, such as a 1-alkyl
body of barbituric or 2-thiobarbituric, e.g., the 1-methyl or
1-ethyl body thereof, a 1,3-dialkyl body of barbituric or
2-thiobarbituric acid, e.g., the 1,3-dimethyl, 1,3-diethyl or
1,3-dibutyl body thereof, a 1,3-diaryl body of barbituric or
2-thiobarbituric acid, e.g., the 1,3-diphenyl,
1,3-di(p-chlorophenyl) or 1,3-di(p-ethoxycarbonylphenyl) body
thereof, a 1-alkyl-1-aryl body of barbituric or 2-thiobarbituric
acid, e.g., the 1-ethyl-3-phenyl body thereof, and barbituric or
2-thiobarbituric acid substituted by heterocyclic groups at the 1-
and 3-positions, e.g., the 1,3-di(2-pyridyl) body of barbituric or
2-thiobarbituric acid).
[0081] More specifically, the nuclei illustrated below and
derivatives thereof are suitable examples of acidic nuclei
represented by formula (B): 2324
[0082] wherein X.sup.C represents an oxygen atom, a sulfur atom,
N--R.sup.C1 or CR.sup.C2R.sup.C3; R.sup.C1, R.sup.C2 and R.sup.C3
each represent a hydrogen atom or a substituent group; Y.sup.C1 and
Y.sup.C2 each represent a nitrogen atom or C--R.sup.C4; R.sup.C4
represents a hydrogen atom or a substituent group, examples of
which include the groups recited above as substituent groups of
R.sup.1, R.sup.2 and R.sup.3 each; and Z.sup.C represents atoms
completing a 5, 6 or 7-membered ring, preferably constituted of any
of carbon, nitrogen, oxygen and sulfur atoms, which may further
form a condensed ring. Additionally, R.sup.C1, R.sup.C2 and
R.sup.C3 have the same meanings as the foregoing R.sup.A1, R.sup.A2
and R.sup.A3 respectively.
[0083] Examples of an acidic nucleus represented by formula (C)
include pyrazolone nuclei, isooxazolinone nuclei, oxazolinone
nuclei, furanone nuclei, oxyindole nuclei, imidazolidone nuclei and
1,2,3,6-tetrahydropyridine-2,6-dione nuclei.
[0084] More specifically, the nuclei illustrated below and
derivatives thereof are recited as acidic nuclei of formula (C)
2526
[0085] wherein X.sup.D represents an oxygen atom, a sulfur atom,
N--R.sup.D1 or CR.sup.D2R.sup.D3, R.sup.D1, R.sup.D2 and R.sup.D3
each represents a hydrogen atom or a substituent group, and Z.sup.D
represents atoms completing a 5, 6 or 7-membered ring, preferably
constituted of any of carbon, nitrogen, oxygen and sulfur atoms.
Additionally, R.sup.D1, R.sup.D2 and R.sup.D3 have the same
meanings as the foregoing R.sup.A1, R.sup.A2 and R.sup.A3
respectively.
[0086] Examples of an acidic nucleus represented by formula (D)
include the nuclei illustrated below and derivatives thereof.
27
[0087] wherein X.sup.E represents an oxygen atom, a sulfur atom,
N--R.sup.E1 or CR.sup.E2 R.sup.E3; R.sup.E1, R.sup.E1 and R.sup.E3
each represent a hydrogen atom or a substituent group; Y.sup.E1 and
Y.sup.E2 each represent a nitrogen atom or C--R.sup.E4; R.sup.E4
represents a hydrogen atom or a substituent group, examples of
which include the groups recited above as substituent groups of
R.sup.1, R.sup.2 and R.sup.3 each; and Z.sup.E represents atoms
completing a 5, 6 or 7-membered ring, preferably constituted of any
of carbon, nitrogen, oxygen and sulfur atoms, which may further
form a condensed ring. Additionally, R.sup.E1, R.sup.E2 and
R.sup.E3 have the same meanings as the foregoing R.sup.A1, R.sup.A2
and R.sup.A3 respectively.
[0088] Examples of an acidic nucleus represented by formula (E)
include the nuclei illustrated below and derivatives thereof.
28
[0089] wherein X.sup.F1 and X.sup.F2 each represent an oxygen atom,
a sulfur atom, N--R.sup.F1 or CR.sup.F2R.sup.F3, R.sup.F1, R.sup.F2
and R.sup.F3 each represent a hydrogen atom or a substituent group,
and Y.sup.F1 and Y.sup.F2 each represent a nitrogen atom or
C--R.sup.F5. Additionally, R.sup.F1 and R.sup.F5 each have the same
meaning as the foregoing R.sup.A1, and R.sup.F2 and R.sup.F3 have
the same meanings as R.sup.A2 and R.sup.A3 respectively. Examples
of an acidic nucleus of formula (F) include
2-thio-2,4-thiazolidinedione nuclei (such as rhodanine and
derivatives thereof, with examples including rhodanines substituted
by an aliphatic hydrocarbon group at the 3-position, such as
3-methylrhodanine, 3-ethylrhodanine and 3-allylrhodanine, those
substituted by an aryl group at the 3-position, such as
3-phenylrhodanine, and those substituted by a heterocyclic group at
the 3-position, such as 3-(2-pyridyl)rhodanine),
2-thio-2,4-oxazolidinedinone nuclei,
2-thio-2,4-(3H,5H)-oxazoledione nuclei, 2-thio-2,5-thiazolidinedi-
one nuclei, 2,4-thiazolidinedione nuclei, thiazoline-4-one nuclei,
4-thiazolidinone nuclei, 2,4-imidazolidinedione (hydantoin) nuclei,
imidazoline-5-one nuclei, and analogues-thereof. More specifically,
the nuclei illustrated below are recited as acidic nuclei of
formula (F). 29
[0090] wherein X.sup.G represents an oxygen atom, a sulfur atom,
N--R.sup.G1 or CR.sup.G2R.sup.G3; R.sup.G1, R.sup.G2 and R.sup.G3
each represent a hydrogen atom or a substituent group; Y.sup.G1 and
Y.sup.G2 each represent a nitrogen atom or C--R.sup.G4; R.sup.G4
represents a hydrogen atom or a substituent group, examples of
which include the groups recited above as substituent groups of
R.sup.1, R.sup.2 and R.sup.3 each; m.sub.1 represents 1 or 2; and
Z.sup.G represents atoms completing a 5, 6 or 7-membered ring,
preferably constituted of any of carbon, nitrogen, oxygen and
sulfur atoms, which may further form a condensed ring.
Additionally, R.sup.G1, R.sup.G2 and R.sup.G3 have the same
meanings as the foregoing R.sup.A1, R.sup.A2 and R.sup.A3
respectively.
[0091] Examples of an acidic nucleus represented by formula (G)
include the nuclei illustrated below. 30
[0092] Further, one of acidic nuclei represented by formula (A) and
another of them may undergo condensation at the site of
.dbd.X.sup.A. To take the case of a rhodanine nucleus represented
by formula (F) in illustration, the following nuclei can be adduced
as examples of such condensation. 3132
[0093] As suitable examples of acidic nuclei represented by formula
(A), preferably including acidic nuclei of formulae (B) to (G),
mention may be made of 1,3-indanedione nuclei, 3,5-pyrazolinedione
nuclei, 1,3-cyclohezanedione nuclei (including their thioketone
bodies), 1,3-dioxane-4,6-dione nuclei,
2,4,6-triketohexahydropyrimidine nuclei (including their thioketone
bodies), pyrazolone nuclei, isooxazolinone nuclei, oxazolinone
nuclei, furanone nuclei, oxyindole nuclei, imidazolidone nuclei,
1,2,3,6-tetrahydropyridine-2,6-dione nuclei, benzothiophene-3-one
nuclei, oxobenzothiophene-3-one nuclei, dioxobenzothiophene-3-one
nuclei, coumaranone nuclei, 1-indanone nuclei, .alpha.-tetralone
nuclei, 2-thio-2,4-thiazolidinedione nuclei,
2-thio-2,4-oxazolidinedione nuclei, 2-thio-2,5-thiazolidinedione
nuclei, 2,4-thiazolidinedione nuclei, 2,4-imidazolidinedione
nuclei, 2-thio-2,4-imidazolidinedione nuclei and 2-imidzoline-5-one
nuclei. Of these nuclei, 1,3-indanedione nuclei,
2,4,6-triketo-hexahydropyrimidine nuclei (including their
thioketone bodies), pyrazolone nuclei, isooxazolinone nuclei,
oxazolinone nuclei, furanone nuclei, oxyindole nuclei, 1-indaznone
nuclei, imidazolidone nuclei, 1,2,3,6-tetrahydropyrid-
ine-2,6-dione nuclei, benzothiophene-3-one nuclei,
oxobenzothiophene-3-one nuclei, dioxobenzo-thiophene-3-one nuclei,
coumaranone nuclei, 2-thio-2,4-thiazolidinedione nuclei,
2-thio-2,4-oxazolidinedione nuclei, 2-thio-2,5-thiazolidinedione
nuclei and 2,4-thiazolidinedione nuclei are preferred over the
others. In particular, 1,3-indanedione nuclei, barbituric acid
derivatives, 2-thiobarbituric acid derivatives, pyrazolone nuclei,
isooxazolinone nuclei, oxazolinone nuclei, furanone nuclei,
1-indanone nuclei, imidazolidone nuclei, 1,2,3,6-tetrahydropyridi-
ne-2,6-dione nuclei, oxobenzothiophene-3-one nuclei,
dioxobenzothiophene-3-one derivatives, 2-thio-2,4-thiazolidinedione
nuclei and 2-thio-2,4-oxazolidinedione nuclei are advantageous over
the others.
[0094] Next, the compound represented by formula (III) is described
below in detail.
[0095] R.sup.1 and R.sup.2 in Formula (III) may be the same or
different, and they each represent an aryl group, a heterocyclic
group or an aliphatic hydrocarbon group, provided that at least
either of them represents an aryl or heterocyclic group.
[0096] The aryl group, heterocyclic group or aliphatic hydrocarbon
group represented by R.sup.1 and R.sup.2 in Formula (III) is the
same as the aryl group, heterocyclic group or aliphatic hydrocarbon
group represented by R.sup.1, R.sup.2 and R.sup.3 in Formula
(I)
[0097] Additionally, R.sup.1 and R.sup.2 may combine with each
other to complete a 5, 6 or 7-membered ring.
[0098] R.sup.7 represents a substituent group and n represents an
integer of 0 to 4. When n is 2, 3 or 4, two to four R.sub.3 groups
may be the same or different. R.sup.4, R.sup.5 and R.sup.6 each
represent a hydrogen atom or a substituent group. Any two of the
substituent groups R.sup.4, R.sup.5, R.sup.6 and R.sup.7 may be
combined with each other to complete a ring. Examples of these
substituent groups include the groups recited above as the
substituent groups which the aryl, heterocyclic or aliphatic
hydrocarbon group represented by R.sup.1 and R.sup.2 each can have.
m represents 0, 1 or 2.
[0099] It is desirable that m be 0 or 1, preferably 0.
[0100] Z.sup.11 represents atoms forming a 5, 6 or 7-membered ring,
which may have another ring in a fused state. Suitable examples of
the ring formed include rings employed as acidic nuclei in
conventional merocyanine dyes. Of such nuclei, the acidic nuclei
represented by formulae (A1) to (G1) respectively, which are
illustrated hereinafter, are preferred over the others.
[0101] Next, the compound represented by formula (IV) is
illustrated below.
[0102] R.sup.1, R.sup.2, R.sup.4 to R.sup.7, m and n in formula
(IV) have the same meanings as in formula (III), respectively. The
acidic nucleus in formula (IV), which is derived from a cyclic
compound of the following formula (A1), is a preferable one among
all the acidic nuclei which can be represented by Z.sup.11 in
formula (III); 33
[0103] wherein X.sub.A represents an oxygen atom, a sulfur atom,
N--R.sub.A1 or CR.sub.A2R.sub.A3; R.sub.A1, R.sub.A2 and R.sub.A3
each represent a hydrogen atom or a substituent group; and Z.sub.A1
represents atoms forming a 5, 6 or 7-membered ring, preferably a 5,
6 or 7-membered ring constituted of any of carbon, nitrogen, oxygen
and sulfur atoms.
[0104] It is desirable that the substituent group represented by
R.sub.A1 be an aliphatic hydrocarbon group, an aryl group or a
heterocyclic group.
[0105] The aliphatic hydrocarbon group represented by R.sub.A1 is a
straight-chain, branched or cyclic alkyl group (containing
preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon
atoms, particularly preferably 1 to 12 carbon atoms, such as
methyl, ethyl, iso-propyl, tert-butyl, n-octyl, n-decyl,
n-hexadecyl, cyclopropyl, cyclopentyl or cyclohexyl), an alkenyl
group (containing preferably 2 to 30 carbon atoms, more preferably
2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms,
such as vinyl, allyl, 2-butenyl or 3-pentenyl) or an alkynyl group
(containing preferably 2 to 30 carbon atoms, more preferably 2 to
20 carbon atoms, particularly preferably 2 to 12 carbon atoms, such
as propargyl or pentynyl), preferably an alkyl group or an alkenyl
group, more preferably methyl, ethyl, propyl, butyl or allyl
group.
[0106] The aryl group represented by R.sub.A1 is preferably a
monocyclic or bicyclic aryl group containing 6 to 30 carbon atoms
(such as phenyl or naphtyl), more preferably a phenyl group
containing 6 to 20 carbon atoms, particularly preferably a phenyl
group containing 6 to 12 carbon atoms.
[0107] The heterocyclic group represented by R.sub.A1 is a
saturated or unsaturated 3- to 10-membered heterocyclic group
containing at least one N, O or S atom. The heterocyclic ring
therein may be a single ring or may further be fused with another
ring to form a condensed ring.
[0108] It is desirable that the heterocyclic group be a 5 or
6-membered aromatic heterocyclic group, preferably a
nitrogen-containing 5 or 6-membered aromatic heterocyclic group,
particularly preferably a 5 or 6-membered aromatic heterocyclic
group containing one to two nitrogen atoms.
[0109] As examples of heterocyclic rings from which the foregoing
heterocyclic groups are derived, mention may be made of
pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan,
pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine,
triazole, triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole, oxadiazole, quinoline,
isoquinoline, phthalazine, naphthylizine, quinoxaline, quinazoline,
cinnoline, pteridine, acridine, phenanthroline, phenazine,
tetrazole, benzimidazole, benzoxazole, benzothiazole, benzotriazole
and tetraazaindene. Of these heterocyclic rings, pyrrole,
imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
triazine, indole, indazole, thiadiazole, oxadiazole, quinoline,
phthalazine, quinoxaline, quinazoline, cinnoline, tetrazole,
thiazole, oxazole, benzimidazole, benzoxazole, benzothiazole and
benzotriazole are preferred over the others. Further, imidazole,
pyridine, quinoline, thiazole, oxazole, benzoimidazole,
benzoxazole, benzothiazole and benzotriazole, especially pyridine
and quinoline, are advantageous.
[0110] The aliphatic hydrocarbon, aryl or heterocyclic group
represented by R.sub.A1 may have a substituent group. Examples of
such a substituent group include the groups recited above as a
substituent group which R.sup.1 and R.sup.2 each can have.
[0111] The groups preferred as R.sub.A1 are an alkyl group, an
alkenyl group and an aryl group, especially alkyl and phenyl
groups.
[0112] R.sub.A2 and R.sub.A3 each are preferably a hydrogen atom, a
cyano group, an oxycarbonyl group, an acyl group, a sulfonyl group,
a thioether group, a carbamoyl group or a sulfamoyl group
(excluding the case of R.sub.A2=R.sub.A3=a hydrogen atom).
[0113] The oxycarbonyl, acyl, sulfonyl or thioether group
represented by R.sub.A2 and R.sub.A3 each is respectively an
oxycarbonyl, acyl, sulfonyl or thioether group substituted by an
aliphatic hydrocarbon, aryl or heterocyclic group. These aliphatic
hydrocarbon, aryl and heterocyclic substituents have the same
meanings as the foregoing aliphatic hydrocarbon, aryl and
heterocyclic groups R.sub.A1 can represent, respectively.
[0114] The carbamoyl or sulfamoyl group represented by R.sub.A2 and
R.sub.A3 each is respectively a carbamoyl or sulfamoyl group having
no substituent or an aliphaptic hydrocarbon, aryl or heterocyclic
substituent. These aliphatic hydrocarbon, aryl and heterocyclic
substituents have the same meanings as the foregoing aliphatic
hydrocarbon, aryl and heterocyclic groups R.sub.A1 can represent,
respectively.
[0115] Next, the compound represented by formula (V) is illustrated
below.
[0116] R.sup.1, R.sup.2, R.sup.4 to R.sup.6, m and n in formula (V)
have the same meanings as in formula (III), respectively. The
acidic nucleus in formula (V), which is derived from a cyclic
compound represented by the following formula (B1), is favorable
one among all the acidic nuclei which can be represented by formula
(A1): 34
[0117] wherein X.sub.B1 and X.sub.B2 each represent an oxygen atom,
a sulfur atom, N--R.sub.B1 or CR.sub.B2R.sub.B3; R.sub.B1, R.sub.B2
and R.sub.B3 each represent a hydrogen atom or a substituent group;
and Z.sub.B1 represents atoms forming a 5, 6 or 7-membered ring,
preferably a 5, 6 or 7-membered ring constituted of any of carbon,
nitrogen, oxygen and sulfur atoms. R.sub.B1, R.sub.B2 and R.sub.B3
have the same meanings as the aforementioned R.sub.A1, R.sub.A2 and
R.sub.A3 respectively. Examples of an acidic nucleus represented by
formula (B1) include substituted 1,3-indanedione nuclei,
heterocyclic ring-condensed cyclopenta-1,3-dione nuclei (the
heterocyclic ring of which is, e.g., pyridine, pyrazine or
thiophene), 3,5-pyrazolinedione nuclei, 1,3-cyclohexanedione
nuclei, 1,3-dioxane-4,6-dione nuclei,
2,4,6-triketohexahydropyrimidine nuclei [e.g., barbituric acid,
2-thiobarbituric acid, and derivatives thereof, such as those
substituted by an alkyl group (e.g., methyl, ethyl) at the
1-position, those substitutedbyalkyl groups (e.g., methyl, ethyl,
butyl) at the 1- and 3-positions respectively, those substituted by
aryl groups (e.g., phenyl, p-chlorophenyl), p-ethoxycarbonylphenyl)
at the 1- and 3-positions respectively, those substituted by alkyl
and aryl groups at the 1- and 3-positions (e.g.,
1-ethyl-3-phenylbarbituric acid, 1-ethyl-3-phenyl-2-thiobarbituric
acid), and those substituted by heterocyclic groups at the 1- and
3-positions respectively (e.g., 1,3-di(2-pyridyl)barbituric acid,
1,3-di(2-pyridyl)-2-thiobarbituric acid)].
[0118] More specifically, the acidic nucleus represented by formula
(B1) include the compounds illustrated below and derivatives
thereof. Additionally, the term "a substituted 1,3-indanedione
nucleus" refers to the 1,3-indanedione nucleus having a substituent
group or another ring condensed thereon.
[0119] Examples of such a substituent group include an alkyl group,
an aryl group, a heterocyclic group, an alkenyl group and a silyl
group. 3536
[0120] Next, the compound represented by formula (VI) is
illustrated below.
[0121] R.sup.1, R.sup.2, R.sup.4 to R.sup.6, m and n in formula
(VI) have the same meanings as in formula (III), respectively. The
acidic nucleus in formula (VI), which is derived from a cyclic
compound represented by the following formula (C1), is favorable
one among all the acidic nuclei which can be represented by formula
(A1): 37
[0122] wherein X.sub.C represents an oxygen atom, a sulfur atom,
N--R.sub.C1 or CR.sub.C2R.sub.C3; R.sub.C1, R.sub.C2 and R.sub.C3
each represent a hydrogen atom or a substituent group; Y.sub.C1 and
Y.sub.C2 each represent a nitrogen atom or C--R.sub.C4; R.sub.C4
represents a hydrogen atom or a substituent group, examples of
which include the groups recited hereinbefore as substituent groups
R.sub.1 and R.sub.2 may have; and Z.sub.C1 represents atoms
completing a 5, 6 or 7-membered ring, preferably a 5, 6 or
7-membered ring constituted of any of carbon, nitrogen, oxygen and
sulfur atoms. R.sub.C1, R.sub.C2 and R.sub.C3 have the same
meanings as R.sub.A1, R.sub.A2 and R.sub.A3 respectively.
[0123] Examples of an acidic nucleus represented by formula (C1)
include an isooxazolinone nucleus, an oxazolinone nucleus, a
furanone nucleus, an oxyindole nucleus, an imidazolidone nucleus
and a 1,2,3,6-tetrahydropyrid- ine-2,6-dione nucleus. More
specifically, these nuclei include the compounds illustrated below
and derivatives thereof. 38
[0124] Further, the compound represented by formula (VII) is
illustrated below.
[0125] R.sup.1, R.sup.2, R.sup.4 to R.sup.6, n and m in formula
(VII) have the same meanings as in formula (III), respectively. The
acidic nucleus in formula (VII), which is derived from a cyclic
compound represented by the following formula (D1), is favorable
one among all the acidic nuclei which can be represented by formula
(A1): 39
[0126] wherein X.sub.D represents an oxygen atom, a sulfur atom,
N--R.sub.D1 or CR.sub.D2R.sub.D3; R.sub.D1, R.sub.D2 and R.sub.D3
each represent a hydrogen atom or a substituent group, and they
have the same meaning as R.sub.A1, R.sub.A2 and R.sub.A3
respectively; Z.sub.D1 represents atoms completing a 5, 6 or
7-membered ring, preferably a 5, 6 or 7-membered ring constituted
of any of carbon, nitrogen, oxygen and sulfur atoms; and R.sub.D
represents a substituent group, including the substituent groups
recited hereinbefore R.sup.1 and R.sup.2 may have; and d represents
an integer of 0 to 4, wherein when d is 2, 3 or 4 the R.sub.D
groups are the same or different. Examples of an acidic nucleus
represented by formula (D1) include the following cyclic compounds
and derivatives thereof. 40
[0127] Furthermore, the compound represented by formula (VIII) is
illustrated below.
[0128] R.sup.1, R.sup.2, R.sup.4 to R.sup.6, n and m in formula
(VIII) have the same meanings as in formula (III), respectively.
The acidic nucleus in formula (VIII), which is derived from a
cyclic compound represented by the following formula (E1), is
favorable one among all the acidic nuclei which can be represented
by formula (A1): 41
[0129] wherein X.sub.E represents an oxygen atom, a sulfur atom,
N--R.sub.E1 or CR.sub.E2R.sub.E3; R.sub.E1, R.sub.E2 and R.sub.E3
each represent a hydrogen atom or a substituent group; Y.sub.E1 and
Y.sub.E2 each represent a nitrogen atom or C--R.sub.E4; R.sub.E4
represents a hydrogen atom or a substituent group, examples of
which include the groups recited hereinbefore as substituent groups
R.sub.1 and R.sub.2 may have; and Z.sub.E1 represents atoms
completing a 5, 6 or 7-membered ring, preferably a 5, 6 or
7-membered ring constituted of any of carbon, nitrogen, oxygen and
sulfur atoms. R.sub.E1, R.sub.E2 and R.sub.E3 have the same
meanings as R.sub.A1, R.sub.A2 and R.sub.A3 respectively.
[0130] Examples of an acidic nucleus represented by formula (E1)
include the following cyclic compounds and derivatives thereof.
42
[0131] Then, the compound represented by formula (IX) is
illustrated below.
[0132] R.sup.1, R.sup.2, R.sup.4 to R.sup.6, n and m in formula
(IX) have the same meanings as in formula (III), respectively. The
acidic nucleus in formula (IX), which is derived from a cyclic
compound represented by the following formula (F1), is favorable
one among all the acidic nuclei which can be represented by formula
(A1): 43
[0133] wherein X.sub.F1 and X.sub.F2 each represents an oxygen
atom, a sulfur atom, N--R.sub.F1 or CR.sub.F2R.sub.F3; R.sub.F1,
R.sub.F2 and R.sub.F3 each represent a hydrogen atom or a
substituent group; Y.sub.F1 and Y.sub.F2 each represent an oxygen
atom, a sulfur atom or N--R.sub.F5; R.sub.F1 and R.sub.F5 each have
the same meaning as R.sub.A1; and R.sub.F2 and R.sub.F3 have the
same meanings as R.sub.A2 and R.sub.A3 respectively.
[0134] As examples of an acidic nucleus represented by formula
(F1), mention may be made of 2-thio-2,4-thiazolidinedione nuclei
(including rhodanine and derivatives thereof, e.g., a rhodanine
substituted by an aliphatic hydrocarbon group at the 3-position,
such as 3-methylrhodanine, 3-ethylrhodanine or 3-allylrhodanine, a
rhodanine substituted by an aryl group at the 3-position, such as
3-phenylrhodanine, and a rhodanine substituted by a heterocyclic
group at the 3-position, such as 3-(2-pyridyl) rhodanine),
2-thio-2,4-oxazolidinedione nuclei, 2-thio-2,4-(3H,5H)-oxazoledione
nuclei, 2-thio-2,5-thiazolidinedione nuclei, 2,4-thiazolidinedione
nuclei, thiazoline-4-one nuclei, 4-thiazolidinone nuclei,
2,4-imidazolidinedione (hydantoin) nuclei,
2-thio-2,4-imidazolidinedione (2-thiohydantoin) nuclei,
imidazoline-5-one nuclei and analogues thereof.
[0135] More specifically, the heterocyclic compounds illustrated
below are included in the acidic nuclei represented by formula
(F1): 44
[0136] In addition, the compound represented by formula (X) is
illustrated below.
[0137] R.sup.1, R.sup.2, R.sup.4 to R.sup.6, n and m in formula (X)
have the same meanings as in formula (III), respectively. The
acidic nucleus in formula (X), which is derived from a cyclic
compound represented by the following formula (G1), is favorable
one among all the acidic nuclei which can be represented by formula
(A1): 45
[0138] wherein X.sub.G represents an oxygen atom, a sulfur atom,
N--R.sub.G1 or CR.sub.G2R.sub.G3; R.sub.G1, R.sub.G2 and R.sub.G3
each represent a hydrogen atom or a substituent group; Y.sub.G1 and
Y.sub.G2 each represent a nitrogen atom or C--R.sub.G4; R.sub.G4
represents a hydrogen atom or a substituent group, examples of
which include the groups recited hereinbefore as substituent groups
R.sup.1 and R.sup.2 may have; m.sub.1 represents 1 or 2; Z.sub.G1
represents atoms completing a 5, 6 or 7-membered ring, preferably a
5, 6 or 7-membered ring constituted of any of carbon, nitrogen,
oxygen and sulfur atoms. Additionally, R.sub.G1, R.sub.G2 and
R.sub.G3 have the same meanings as R.sub.A1, R.sub.A2 and R.sub.A3
defined hereinbefore, respectively.
[0139] Examples of an acidic nucleus represented by formula (G1)
are as follows: 46
[0140] Besides the acidic nuclei as recited above, the 5, 6 or
7-membered ring represented by Z.sup.11 in formula (III) may be an
acidic nucleus formed by condensing the moiety .dbd.X.sub.A in
formula (A1) and an acidic nucleus represented by formula (A1). To
take examples from the rhodanine nuclei represented by formula
(F1), the acidic nuclei formed by such a condensation are as
follows; 4748
[0141] Suitable examples of acidic nuclei represented by formulae
(A1) to (G1) include substituted 1,3-indanedione nuclei,
heterocyclic ring-condensed cyclopentane-1,3-dione nuclei,
3,5-pyrazolinedionedione nuclei, 1,3-cyclohexanedione nuclei
(including thioketone bodies), 1,3-dioxane-4,6-dione nuclei,
2,4,6-triketohexahydropyrimidine nuclei, isooxazolinone nuclei,
oxazolinone nuclei, furanone nuclei, oxyindole nuclei,
imidazolidone nuclei, 1,2,3,6-tetrahydropyridine-2,6-dione nuclei,
benzothiophene-2-one nuclei, oxobenzothiophene-3-one nuclei,
dioxobenzothiophene-3-one nuclei, coumaranone nuclei, 1-indanone
nuclei, .alpha.-tetralone nuclei, 2-thio-2,4-thiazolidinedione
nuclei, 2-thio-2,5-thiazolidinedione nuclei, 2,4-thiazolidinedione
nuclei, 2,4-imidazolidinedione nuclei,
2-thio-2,4-imidazoolidinedione nuclei and 2-imidzoline-5-one
nuclei. Of these nuclei, the preferable nuclei are substituted
1,3-indanedione nuclei, 2,4,6-triketohexahydropyrimidine nuclei
(including thioketo bodies), isooxazolinone nuclei, oxazolinone
nuclei, furanone nuclei, oxyindone nuclei, imidazolidone nuclei,
1,2,3,6-tetrahydropyridine-2,6-dione nuclei, benzothiophene-3-one
nuclei, oxobenzothiophene-3-one nuclei, dioxobenzothiophene-3-one
nuclei, coumaranone nuclei, oxyindole nuclei, 1-indanone nuclei,
2-thio-2,4-thiazolidinedione nuclei, 2-thio-2,4-oxazolidinedione
nuclei, 2-thio-2,5-thiazolidinedione nuclei and
2,4-thiazolidinedione nuclei. In particular, substituted
1,3-indanedione nuclei, barbituric acid derivatives,
2-thiobarbituric acid derivatives, isooxazolinone nuclei,
oxazolinone nuclei, furanone nuclei, imidazolidone nuclei,
1,2,3,6-tetrahydropyridine-2,6-dione nuclei,
oxobenzothiophene-3-one nuclei, dioxobenzothiophene-3-one nuclei,
1-indanone nuclei, 2-thio-2,4-thiazolidinedione nuclei and
2-thio-2,4-oxazolidinedione nuclei are advantageous.
[0142] Next, styrylamine compounds represented by formula (XI) are
illustrated below.
[0143] R.sup.21 and R.sup.22 each in formula (XI) have the same
meaning as the aryl or heterocyclic group represented by R.sup.1
and R.sup.2 each in formula (III). Favorable ranges of these groups
are the same in both formulae. R.sup.27 has the same meaning as
R.sup.7 in formula (III). Z.sup.2 represents a 1,3-indanedione
nucleus having one or more substituent groups (which may complete a
condensed nucleus or each represent an alkyl, aryl, heterocyclic,
alkenyl or silyl group), a furanone nucleus, an oxyindole nucleus,
an imidazolidone nucleus, a dioxobenzothiophene-3-one nucleus, a
coumaranone nucleus, an oxyindole nucleus, a 1-indanone nucleus
having a substituent at the 3-position (wherein the substituent is
an alkyl, aryl or heterocyclic group), a benzofuran-3-one nucleus,
a 2-thio-2,4-thiazolidinedione nucleus, a
2-thio-2,4-oxazolidinedione nucleus, a 2-thio-2,5-thiazolidinedione
nucleus, a 2,4-thiazolidinedione nucleus, 2,4-imidazolidinedione
nucleus, 2-thio-2,4-imidazolidinedione nucleus or a
2-imidazoline-5-one nucleus. The carbonyl oxygen or the
thiocarbonyl sulfur attached to the cyclic skeleton constituting
Z.sup.2 may be replaced with N--R.sup.2a or CR.sup.2bR.sup.2c,
wherein R.sup.2a, R.sup.2b and R.sup.2c each represent a hydrogen
atom or a substituent group, and they have the same meanings as
R.sub.A1, R.sub.A2 and R.sub.A3 in formula (IV) respectively.
[0144] The nuclei preferred as Z.sup.2 include a 1,3-indanedione
nucleus having one or more substituent groups (which may complete a
condensed ring, such as a carbon or heterocyclic ring containing at
most 20 carbon atoms, or each represent a 1-20C alkyl, 6-20C aryl,
1-20C heterocyclic or 2-30C alkenyl group), a
dioxobenzothiophene-3-one nucleus, a benzofuran-3-one nucleus, a
1-indanone nucleus having a substituent at the 3-position (the
substituent of which is a 1-20C alkyl, 6-20C aryl or 1-20C
heterocyclic group) and a 2-thio-2,4-thiazolidinedione nucleus.
[0145] Then, the formula (XII) representing an amine compound is
illustrated below in detail.
[0146] Ar.sup.31 represents an arylene group or a divalent
heterocyclic group, and R.sup.32 represents an aryl group, a
heterocyclic group and an aliphatic hydrocarbon group. These aryl,
heterocyclic and aliphatic hydrocarbon groups have the same
meanings as those represented by R.sup.1, R.sup.2 and R.sup.3 each
in formula (I), respectively. Favorable ranges of these groups are
the same in both formulae.
[0147] R.sup.34, R.sup.35, R.sup.36 and Z.sup.3 have the same
meanings as R.sup.4, R.sup.5, R.sup.6 and Z.sup.1 in formula (II),
respectively. m represents 0, 1 or 2. t represents an integer of at
least 2. One combination made with Ar.sup.31, R.sup.32, R.sup.34,
R.sup.35, R.sup.36, Z.sup.3 and m may be the same as or different
from another combination made therewith. L represents a t-valent
linkage group.
[0148] The suitable linkage group for L is a group constituted of
at least one fragment selected from the class consisting of an
oxygen atom, a nitrogen atom, a sulfur atom, a methylene group, a
vinylene group, an acetylene group, a phenylene group, an aniline
group and a heterocyclic group. The groups recited above may have a
substituent, and those cyclic groups each may form a condensed ring
by fusing together with another ring. The suitable number of carbon
atoms contained in the foregoing heterocyclic group is from 1 to
20, preferably from 1 to 12, and examples of a hetero atom
contained therein include nitrogen, oxygen, sulfur and selenium
atoms. To be concrete, such a heterocyclic group includes the
groups derived from pyrrolidine, piperidine, piperazine,
morpholine, thiophene, selenophene, furan, pyrrole, imidazole,
pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine,
indole, indazole, purine, thiazoline, thiazole, thiadiazole,
oxazoline, oxazole, oxadiazole, quinoline, isoquinoline,
phthalazine, naphthylizine, quinoxaline, quinazoline, cinnoline,
pteridine, acridine, phenanthroline, phenazine, tetrazole,
benzimidazole, benzoxazole, benzothiazole, benzotriazole and
tetrazaindene. And the foregoing substituent includes the groups
recited as substituent groups which R.sup.1, R.sup.2 and R.sup.3
can have.
[0149] It is desirable for L to be a group constituted of at least
one fragment selected from the class consisting of an oxygen atom,
a nitrogen atom, a sulfur atom, a methylene group, a vinylene
group, an acetylene group and groups derived from aniline, benzene,
thiophene, pyrrole, furan, selenophene, imidazole, pyrazole,
pyridine, pyrazine, pyridazine, triazole, triazine, indole,
indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline,
oxazole and oxadiazole nuclei respectively. These nuclei each may
form a condensed ring.
[0150] In particular, the mono- to polymers, preferably the mono-
to eicosamers, more preferably the mono- to decamers, particularly
preferably the mono- to pentamers, of aniline, benzene, thiophene,
pyrrole, furan, selenophene, naphthalene, anthracene, pyridine,
pyridazine, pyrimidine, azulene, carbazole, arylenevinylene,
aryleneetynylene, arylenephenylene and triarylamine respectively
(wherein the arylene moiety and the aryl moiety include the groups
derived from benzene, thiophene, pyrrole, furan, selenophene,
imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole and oxadiazole respectively) are
preferred as L, and thereto an oxygen atom, a nitrogen atom, a
sulfur atom or a methylene group may be attached as a linking
moiety.
[0151] The formula (XIII) representing another amine compound is
illustrated below.
[0152] Ar.sup.41 represents an arylene group or a divalent
heterocyclic group, and R.sup.42 represents an aryl group, a
heterocyclic group and an aliphatic hydrocarbon group. R.sup.44,
R.sup.45 and R.sup.46 each represent a hydrogen atom or a
substituent group. These Ar.sup.41, R.sup.42, R.sup.44, R.sup.45,
R.sup.46 and Z.sup.4 have the same meanings as Ar.sup.31, R.sup.32,
R.sup.34, R.sup.35, R.sup.36 and Z.sup.3 in formula (XII),
respectively. m represents 0, 1 or 2. p represents 2 or 3. One
combination made with Ar.sup.41, R.sup.42, R.sup.44, R.sup.45,
R.sup.46, Z.sup.4 and m may be the same as or different from
another combination made therewith.
[0153] Then, the formula (XIV) is described below. R.sup.54,
R.sup.55 and R.sup.56 each represent a hydrogen atom or a
substituent group. R.sup.57 and R.sup.58 each represent a
substituent group. q represents an integer of 0 to 4, and r
represents an integer of 0 to 5. When q is 2, 3 or 4, the R.sup.57
groups may be the same or different; while, when r is 2, 3, 4 or 5,
the R.sup.58 groups may be the same or different. Examples of a
substituent group represented by R.sup.54, R.sup.55, R.sup.56,
R.sup.57 and R.sup.58 each include the groups recited above as
substituents which the aryl, heterocyclic or aliphatic hydrocarbon
group represented by R.sup.1, R.sup.2 and R.sup.3 each can have.
Z.sup.5 represents atoms forming a 5, 6 or 7-membered ring, and has
the same meaning as Z.sup.1 in formula (II). m represents 0, 1 or
2. t represents an integer of at least 2. One combination made with
R.sup.54, R.sup.55, R.sup.56, R.sup.57, R.sup.58, Z.sup.5, m, q and
r may be the same as or different from another combination made
therewith. L represents a t-valent linkage group, and has the same
meaning as L in formula (XII).
[0154] Further, the formula (XV) is described below. R.sup.62
represents an aryl group, a heterocyclic group or an aliphatic
hydrocarbon group, and has the same meaning as the aryl,
heterocyclic or aliphatic hydrocarbon group represented by R.sup.1,
R.sup.2 and R.sup.3 each in formula (I). R.sup.64, R.sup.65 and
R.sup.66 each represent a hydrogen atom or a substituent group.
R.sup.67 represents a substituent group, and q represents an
integer of 0 to 4. When q is 2, 3 or 4, the R.sup.67 groups may be
the same or different. Z.sup.6 represents atoms forming a 5, 6 or
7-membered ring. R.sup.64, R.sup.65, R.sup.66, R.sup.67 and Z.sup.6
have the same meanings as R.sup.54, R.sup.55, R.sup.56, R.sup.67
and Z.sup.5, respectively. m represents 0, 1 or 2. p represents 2
or 3. One combination made with R.sup.62, R.sup.64, R.sup.65,
R.sup.66, R.sup.67, Z.sup.6, m and q may be the same as or
different from another combination made therewith.
[0155] Furthermore, the formula (XVI) is described below. R.sup.74
represents a hydrogen atom or a substituent group. R.sup.77 and
R.sup.78 each represent a substituent group. q represents an
integer of 0 to 4, and r represents an integer of 0 to 5. When q is
2, 3 or 4, the R.sup.77 groups may be the same or different; while,
when r is 2, 3, 4 or 5, the R.sup.78 groups may be the same
ordifferent. Z.sup.7 represents atoms forming a 5, 6 or 7-membered
ring. R.sup.74, R.sup.77, R.sup.78 and Z.sup.7 have the same
meanings as R.sup.54, R.sup.57, R.sup.58 and Z.sup.5 in formula
(XIV), respectively. t represents an integer of at least 2. One
combination made with R.sup.74, R.sup.75, R.sup.76, R.sup.77,
R.sup.78, Z.sup.7, q and r may be the same as or different from
another combination made therewith. L represents a t-valent linkage
group, and has the same meaning as L in formula (XII).
[0156] In addition, the formula (XVII) is described below. R.sup.84
represents a hydrogen atom or a substituent group. R.sup.87 and
R.sup.88 each represent a substituent group. q represents an
integer of 0 to 4, and r represents an integer of 0 to 5. When q is
2, 3 or 4, the R.sup.87 groups may be the same or different; while,
when r is 2, 3, 4 or 5, the R.sup.88 groups may be the same or
different. R.sup.14, R.sup.87 and R.sup.88 have the same meanings
as R.sup.54, R.sup.57 and R.sup.58 in formula (XIV), respectively.
Z.sup.8 represents atoms forming a 5, 6 or 7-membered ring. X.sup.8
represents an oxygen atom, a sulfur atom, N--R.sup.A1 or
CR.sup.A2R.sup.A3, and R.sup.A1, R.sup.A2 and R.sup.A3 each
represent a hydrogen atom or a substituent group. Z.sup.8 and
X.sup.8 have the same meanings as Z.sup.A and X.sup.A respectively
in formula (A), which constitute the acidic nucleus as one
preferred example of Z.sup.1 in formula (II). t represents an
integer of at least 2. One combination made with R.sup.84,
R.sup.87, R.sup.88, Z.sup.8, X.sup.8, q and r may be the same as or
different from another combination made therewith. L represents a
t-valent linkage group, and has the same meaning as L in formula
(XII).
[0157] Besides the aforementioned formulae, the formula (XVIII) is
described below. R.sup.94 represents a hydrogen atom or a
substituent group. R.sup.97 and R.sup.98 each represent a
substituent group. q represents an integer of 0 to 4, and r
represents an integer of 0 to 5. When q is 2, 3 or 4, the R.sup.97
groups may be the same or different; while, when r is 2, 3, 4 or 5,
the R.sup.98 groups may be the same or different. Z.sup.9
represents atoms forming a 5, 6 or 7-membered ring. X.sup.9
represents an oxygen atom, a sulfur atom, N--R.sup.A1 or
CR.sup.A2R.sup.A3, and R.sup.A1, R.sup.A2 and R.sup.A3 each
represent a hydrogen atom or a substituent group. R.sup.94,
R.sup.97, R.sup.98, Z.sup.9 and X.sup.9 have the same meanings as
R.sup.84, R.sup.87, R.sup.88; Z.sup.8 and X.sup.8 in formula (XVII)
respectively. t represents an integer of at least 2. One
combination made with R.sup.94, R.sup.97, R.sup.98, Z.sup.9,
X.sup.9, q and r may be the same as or different from another
combination made therewith. L represents a t-valent linkage group,
and has the same meaning as L in formula (XII).
[0158] The compounds represented by formula (I) or those
represented by any of formulae (III) to (XVIII) may be low
molecular weight compounds, or may be high molecular weight
compounds having a structure that the compound residue is connected
to each constitutional unit of the polymer main chain (the weight
average molecular weight of which is preferably from 1,000 to
5,000,000, more preferably from 5,000 to 2,000,000, particularly
preferably from 10,000 to 1,000,000) or high molecular weight
compounds having a structure that the skeletons represented by
formula (I) or those represented by any of formulae (III) to
(XVIII) are present in their main chain (the weight average
molecular weight of which is preferably from 1,000 to 5,000,000,
more preferably from 5,000 to 2,000,000, particularly preferably
from 10,000 to 1,000,000). Such high molecular weight compounds may
be homopolymers, or copolymers of the aforementioned compounds and
other monomers.
[0159] It is preferable that the compounds represented by formula
(I), specifically including the compounds represented by formulae
(III) to (XVIII), are low molecular weight compounds. Additionally,
the formulae (II) to (XVIII) are each expressed in extreme
structure for convenience's sake, and so all the compounds
illustrated above may be their respective tautomers.
[0160] The desirable combinations of groups constituting a compound
represented by formula (I) are described below.
[0161] It is desirable that R.sup.1, R.sup.2 and R.sup.3, which may
be the same or different, each be a 6-30C monocyclic or bicyclic
aryl group (e.g., phenyl, naphthyl), a 5 or 6-membered aromatic
heterocyclic group containing as hetero atom(s) any of nitrogen,
oxygen and sulfur atoms or a 1-20C alkyl, alkenyl or alkynyl group,
provided that at least two among R.sup.1, R.sup.2 and R.sup.3 are
each the foregoing aryl or heterocyclic group and at least either
of them has a moiety represented by formula (II) as a substituent
group. And R.sup.1, R.sup.2 and R.sup.3 each may have a substituent
group, such as alkyl, alkenyl, aralkyl, aryl, alkoxy, amino, acyl,
alkoxycarbonyl, aryloxycarbonyl, carbonylamino, sulfonylamino,
sulfamcyl, carbamoyl, hydroxy or heterocyclic group. These groups
each may further be substituted. R.sup.4, R.sup.5 and R.sup.6 in
formula (II) are each a hydrogen atom or a substituent group, such
as an alkyl group, an alkoxy group, an alkylthio group, an alkenyl
group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, a
carbonamido group or a cyano group. It is desirable for Z.sup.1 to
be a ring derived from an acidic nucleus represented by formula
(B), (C), (D), (E), (F) or (G).
[0162] The preferable combinations of groups constituting the
compound represented by formula (I) is represented by formula
(III). The desirable combinations of groups constituting the
compound represented by formula (III) are described below.
[0163] For the compound of formula (III), it is desirable that m is
0, 1 or 2, and R.sup.1 and R.sup.2, which may be the same or
different, each be a 6-30C (carbon atoms: 6-30) monocyclic or
bicyclic aryl group or a 5 or 6-membered heterocyclic group which
contains nitrogen, oxygen or/and sulfur atoms and may have a
substituent group, such as alkyl, alkenyl, aralkyl, alkoxy, amino,
acyl, alkoxycarbonyl, aryloxycarbonyl, carbonylamino,
sulfonylamino, sulfamoyl, carbamoyl, hydroxy or heterocyclic group,
R.sup.7 and R.sup.4 each be a hydrogen atom, an alkyl group, an
alkoxy group, an alkylthio group, an acyl group, a substituted
amino group (the substituent of which is an alkyl, alkenyl,
alkynyl, aryl or heterocyclic group), R.sup.5 and R.sup.6 each be a
hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group,
an alkenyl group, an acyl group, a sulfonyl group, an
alkoxycarbonyl group, a carbonamido group or a cyano group, and
Z.sup.11 be an acidic nucleus derived from a cyclic compound
represented by formula (B1), (C1), (D1), (E1), (F1) or (G1).
[0164] The desirable combinations of groups constituting the
compound represented by formula (IV) are described below.
[0165] For the compound of formula (IV), it is desirable that m be
0 or 1, R.sup.1 and R.sup.2, which may be the same or different,
each be an unsubstituted or substituted phenyl or naphthyl group
containing up to 30 carbon atoms or an unsubstituted or substituted
5 or 6-membered aromatic heterocyclic group containing one to two
nitrogen atoms or/and one to two sulfur atoms (the substituent of
which contains 1 to 20 carbon atoms, such as an alkyl, alkenyl,
aralkyl, aryl, alkoxy, amino, acyl, carbonylamino, sulfonylamino or
heterocyclic group), R.sup.7 and R.sup.4 each be a hydrogen atom, a
1-20C alkyl group, a 1-20C alkoxy group or a 1-20C substituted
amino group (the substituent(s) of which is(are) an alkyl group, an
alkenyl group, an alkynyl group, an aryl group or/and a
heterocyclic group), R.sup.5 and R.sup.6 each be a hydrogen atom, a
1-20C alkyl group, a 2-20C alkenyl group, a 1-20C acyl group, a
1-20C sulfonyl group, a 2-20C alkoxycarbonyl group, a 1-20C
carbonamido group or a cyano group, and Z.sup.11 be a substituted
1,3-indanedione nucleus, a 2,4,6-triketohexahydropyrimidine nucleus
(including a thioketone body), an isooxazolinone nucleus, an
oxazolinone nucleus, a furanone nucleus, an oxyindole nucleus, an
imidazolidone nucleus, a 1,2,3,6-tetrahydropyridine- -2,6-dione
nucleus, a benzothiophene-3-one nucleus, an oxobenzothiophene-3-one
nucleus, a dioxobenzothiophene-3-one nucleus, a coumaranone
nucleus, a 1-indanone nucleus, a 2-thio-2,4-thiazolidinedione
nucleus, a 2-thio-2,4-oxazolidinedione nucleus, a
2-thio-2,5-thiazolidine- dione nucleus or a 2,4-thiazolidinedione
nucleus, especially a substituted 1,3-indanedione nucleus, a
2,4,6-triketohexahydropyrimidine nucleus, a
dioxobenzothiophene-3-one nucleus or a 2-thio-2,5-thiazolidinedione
nucleus.
[0166] Other desirable combinations of groups constituting a
compound represented by formula (I) are those embodied in compounds
represented by formulae (XII) and (XIII), respectively.
[0167] The desirable combinations of constituent groups in formula
(XII) are described below: The Ar.sup.31 groups, which may be the
same or different, each represent a 6-30C monocyclic or bicyclic
arylene group (e.g., phenylene or naphthylene) or a divalent 5 or
6-membered aromatic heterocyclic group containing as hetero atom(s)
any of nitrogen, oxygen and sulfur atoms. R.sup.32 represents a
6-30C monocyclic or bicyclic aryl group (e.g., phenyl, naphthyl), a
5 or 6-membered aromatic heterocyclic group containing as hetero
atom(s) any of nitrogen, oxygen and sulfur atoms, or a 1-20C alkyl,
alkenyl or alkynyl group. The Ar.sup.31 and R.sup.32 groups each
may have a substituent group, such as an alkyl group, an alkoxy
group, an alkylthio group, an acyl group or a substituted amino
group (the substituent of which includes alkyl, alkenyl, alkynyl,
aryl and heterocyclic groups) R.sup.34, R.sup.35 and R.sup.36 are
each a hydrogen atom or a substituent group, such as an alkyl
group, an alkoxy group, an alkylthio group, an alkenyl group, an
acyl group, a sulfonyl group, an alkoxycarbonyl group, a
carbonamido group or a cyano group. Z.sup.3 is any of the rings
represented by formulae (B) to (G) respectively. And L is a group
comprising one nucleus or at least two linked nuclei (polymerized
nuclei), preferably a monomeric to eicosameric group, the nucleus
or nuclei of which are selected from the family consisting of
aniline, benzene, thiophene, pyrrole, furan, selenophene,
naphthalene, anthracene, pyridine, pyridazine, pyrimidine, azulene,
carbazole, arylenevinylene, aryleneethynylene, arylenephenylene and
triarylamine (the arylene or aryl moiety of which is a group
derived from benzene, thiophene, pyrrole, furan, selenophene,
imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole or oxadiazole). Such a nuclei or
nuclei may further be combined with an oxygen, nitrogen, sulfur or
methylene linkage.
[0168] The desirable combinations in formula (XIII) are described
below: The Ar.sup.41 groups, which may be the same or different,
each represent a 6-30C monocyclic or bicyclic arylene group (e.g.,
phenylene or naphthylene) or a divalent or 6-membered aromatic
heterocyclic group containing as hetero atom(s) any of nitrogen,
oxygen and sulfur atoms. R.sup.42 represents a 6-30C monocyclic or
bicyclic aryl group (e.g., phenyl, naphthyl), a 5 or 6-membered
aromatic heterocyclic group containing as hetero atom(s) any of
nitrogen, oxygen and sulfur atoms, or a 1-20C alkyl, alkenyl or
alkynyl group. The Ar.sup.41 and R.sup.42 groups each may have a
substituent group, such as an alkyl group, an alkoxy group, an
alkylthio group, an acyl group or a substituted amino group (the
substituent of which includes alkyl, alkenyl, alkynyl, aryl and
heterocyclic groups) R.sup.44, R.sup.45 and R.sup.46 are each a
hydrogen atom or a substituent group, such as an alkyl group, an
alkoxy group, an alkylthio group, an alkenyl group, an acyl group,
a sulfonyl group, an alkoxycarbonyl group, a carbonamido group or a
cyano group. Z.sup.4 is any of the rings derived from the acidic
nuclei represented by formulae (B) to (G) respectively.
[0169] The more desirable combinations in formula (XII) are
embodied in formula (XIV). The favorable combinations in formula
(XIV) are described below: R.sup.54, R.sup.55 and R.sup.56 are each
a hydrogen atom or a substituent group, such as an alkyl group, an
alkoxy group, an alkylthio group, an alkenyl group, an acyl group,
a sulfonyl group, an alkoxycarbonyl group, a carbonamido group or a
cyano group. Z.sup.5 is any of the rings represented by formulae
(B) to (G) respectively. R.sup.57 and R.sup.58 are each an alkyl
group, an alkoxy group, an alkylthio group, an acyl group or a
substituted amino group (the substituent of which includes an alkyl
group, an alkenyl group, an alkynyl group, an aryl group or a
heterocyclic group). And L is a group comprising one nucleus or at
least two linked nuclei (polymerized nuclei), preferably a
monomeric to eicosameric group, the nucleus or nuclei of which are
selected from the family consisting of aniline, benzene, thiophene,
pyrrole, furan, selenophene, naphthalene, anthracene, pyridine,
pyridazine, pyrimidine, azulene, carbazole, arylenevinylene,
aryleneethynylene, arylenephenylene and triarylamine (the arylene
or aryl moiety of which is a group derived from benzene, thiophene,
pyrrole, furan, selenophene, imidazole, pyrazole, pyridine,
pyrazine, pyridazine, triazole, triazine, indole, indazole, purine,
thiazoline, thiazole, thiadiazole, oxazoline, oxazole or
oxadiazole). Such a nucleus or nuclei may further be combined with
an oxygen, nitrogen, sulfur or methylene linkage.
[0170] The more desirable combinations in formula (XIII) are
embodied in formula (XV). The favorable combinations in formula
(XV) are described below: R.sup.62 represents a 6-30C monocyclic or
bicyclic aryl group (e.g., phenyl, naphthyl), a 5 or 6-membered
aromatic heterocyclic group containing as hetero atom(s) any of
nitrogen, oxygen and sulfur atoms, or a 1-20C alkyl, alkenyl or
alkynyl group. The R.sup.62 group may have a substituent group, and
such a substituent and R.sup.67 are each an alkyl group, an alkoxy
group, an alkylthio group, an acyl group or a substituted amino
group (the substituent of which includes alkyl, alkenyl, alkynyl,
aryl and heterocyclic groups) R.sup.64, R.sup.65 and R.sup.66 are
each a hydrogen atom or a substituent group, such as an alkyl
group, an alkoxy group, an alkylthio group, an alkenyl group, an
acyl group, a sulfonyl group, an alkoxycarbonyl group, a
carbonamido group or a cyano group. And Z.sup.6 is any of the rings
represented by formulae (B) to (G) respectively.
[0171] The more desirable combinations in formula (XIV) are
embodied in formula (XVI). The favorable combinations in formula
(XVI) are described below: R.sup.74 represents a hydrogen atom or a
substituent group, such as an alkyl group, an alkoxy group, an
alkylthio group, an alkenyl group, an acyl group, a sulfonyl group,
an alkoxycarbonyl group, a carbonamido group or a cyano group.
Z.sup.7 represents atoms forming a 5- to 7-membered ring, which may
be fused together with another ring. Suitable examples of such
rings include rings generally employed as acidic nuclei of
merocyanine dyes. R.sup.77 and R.sup.78 are each an alkyl group, an
alkoxy group, an alkylthio group, an acyl group or a substituted
amino group (the substituent of which includes alkyl, alkenyl,
alkynyl, aryl and heterocyclic groups). And L is a group comprising
one nucleus or at least two linked nuclei (polymerized nuclei),
preferably a monomeric to eicosameric group, the nucleus or nuclei
of which are selected from the family consisting of aniline,
benzene, thiophene, pyrrole, furan, selenophene, naphthalene,
anthracene, pyridine, pyridazine, pyrimidine, azulene, carbazole,
arylenevinylene, aryleneethynylene, arylenephenylene and
triarylamine (the arylene or aryl moiety of which is a group
derived from benzene, thiophene, pyrrole, furan, selenophene,
imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole or oxadiazole). Such a nucleus or
nuclei may further be combined with an oxygen, nitrogen, sulfur or
methylene linkage.
[0172] The desirable combinations in formula (XVI) are represented
by formula (XVII). Therein, suitable R.sup.84, R.sup.87, R.sup.88
and L have the same meanings as R.sup.74, R.sup.77, R.sup.78 and L
in formula (XVI) respectively, and the acidic nucleus is a ring
represented by formula (A). The more desirable combinations in
formula (XVII) are described below: R.sup.84 is a hydrogen atom, a
1-20C alkyl group, a 1-20C alkenyl group, a 1-20C acyl group, a
1-20C sulfonyl group, a 1-20C alkoxycarbonyl group, a 1-20C
carbonamido group or a cyano group. R.sup.87 and R.sup.88 are each
a 1-20C alkyl group, a 1-20C alkoxy group or a 1-20C substituted
amino group (the substituent of which includes alkyl, alkenyl,
alkynyl, aryl and heterocyclic groups). The acidic nucleus is a
ring represented by formula (B), (C), (D), (E), (F) or (G),
particularly preferably a 1,3-indanedione nucleus, a
2,4,6-triketohexahydropyrimidine nucleus (including its thioketone
body), a pyrazolone nucleus, an isooxazolinone nucleus, an
oxazolinone nucleus, a furanone nucleus, an oxyindole nucleus, a
1-indanone nucleus, an imidazolidone nucleus, a
1,2,3,6-tetrahydropyridine-2,6-dione nucleus, a
benzothiophene-3-one nucleus, an oxobenzothiophene-3-one nucleus, a
dioxobenzothiophene-3-one nucleus, a coumaranone nucleus, a
2-thio-2,4-thiazolidinedione nucleus, a 2-thio-2,4-oxazolidinedione
nucleus, a 2-thio-2,5-thiazolidinedione nucleus or a
2,4-thiazolidinedione nucleus. And L is a group comprising one
nucleus or at least two linked nuclei (polymerized nuclei),
preferably a monomeric to eicosameric group, the nucleus or nuclei
of which are selected from the family consisting of aniline,
benzene, thiophene, pyrrole, furan, selenophene, naphthalene,
anthracene, pyridine, pyridazine, pyrimidine, azulene, carbazole,
arylenevinylene, aryleneethynylene, arylenephenylene and
triarylamine (the arylene or aryl moiety of which is a group
derived from benzene, thiophene, pyrrole, furan, selenophene,
imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole or oxadiazole). Such a nucleus or
nuclei may further be combined with an oxygen, nitrogen, sulfur or
methylene linkage.
[0173] The desirable combinations in formula (XVIII) are described
below: R.sup.94 is a hydrogen atom, a 1-20C alkyl group, a 1-20C
alkenyl group, a 1-20C acyl group, a 1-20C sulfonyl group, a 1-20C
alkoxycarbonyl group, a 1-20C carbonamido group or a cyano group.
R.sup.97 and R.sup.98 are each a 1-20C alkyl group, a 1-20C alkoxy
group or a 1-20C substituted amino group (the substituent of which
includes alkyl, alkenyl, alkynyl, aryl and heterocyclic groups).
The acidic nucleus is a ring represented by formula (B), (C), (D),
(E), (F) or (G). And L is a group derived from a monomer to a
polymer, preferably a monomer to an eicosamer, of aniline, benzene,
thiophene, pyrrole, furan, selenophene, naphthalene, anthracene,
pyridine, pyridazine, pyrimidine, azulene, carbazole,
arylenevinylene, aryleneethynylene, arylenephenylene or
triarylamine (the arylene or aryl moiety of which is a group
derived from benzene, thiophene, pyrrole, furan, selenophene,
imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole or oxadiazole). Such a group may
further have an oxygen, nitrogen, sulfur or methylene linkage.
[0174] In more desirable combinations, R.sup.94 is a hydrogen atom,
a 1-20C alkenyl group, a 1-20C acyl group, a 1-20C sulfonyl group,
a 1-20C alkoxycarbonyl group, a 1-20C carbonamido group or a cyano
group, while R.sup.97 and R.sup.9 are each a 1-20C alkyl group, a
1-20C alkoxy group or a 1-20C substituted amino group (the
substituent of which includes alkyl, alkenyl, alkynyl, aryl and
heterocyclic groups). The acidic nucleus is a 1,3-indanedione
nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including its
thioketone body), a pyrazolone nucleus, an isooxazolinone nucleus,
an oxazolinone nucleus, a-furanone nucleus, an oxyindole nucleus, a
1-indanone nucleus, an imidazolidone nucleus, a
1,2,3,6-tetrahydropyridine-2,6-dione nucleus, a
benzothiophene-3-one nucleus, an oxobenzothiophene-3-one nucleus, a
dioxobenzothiophene-3-one nucleus, a coumaranone nucleus, a
2-thio-2,4-thiazolidinedione nucleus, a 2-thio-2,4-oxazolidinedione
nucleus, a 2-thio-2,5-thiazolidinedione nucleus or a
2,4-thiazolidinedione nucleus. And L is a group comprising one
nucleus or at least two linked nuclei (polymerized nuclei),
preferably a monomeric to eicosameric group, the nucleus or nuclei
of which are selected from the family consisting of aniline,
benzene, thiophene, pyrrole, furan, selenophene, naphthalene,
anthracene, pyridine, pyridazine, pyrimidine, azulene, carbazole,
arylenevinylene, aryleneethynylene, arylenephenylene and
triarylamine (the arylene or aryl moiety of which is a group
derived from benzene, thiophene, pyrrole, furan, selenophene,
imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole or oxadiazole). Such a nucleus or
nuclei may further be combined with an oxygen, nitrogen, sulfur or
methylene linkage.
[0175] In particularly desirable combinations, R.sup.94 is a
hydrogen atom, a 1-10C alkenyl group, a 1-10C acyl group, a 1-10C
sulfonyl group, a 1-10C alkoxycarbonyl group, a 1-10C carbonamido
group or a cyano group, while R.sup.97 and R.sup.98 are each a
1-10C alkyl group, a 1-10C alkoxy group or a 1-20C substituted
amino group (the substituent of which includes alkyl, alkenyl,
alkynyl, aryl, thiophenyl, pyrrolyl, furanyl, selenophenyl,
naphthyl, anthrayl, pyridyl, pyridazinyl, pyrimidyl, azulenyl and
carbazolyl groups). The acidic nucleus is a 1,3-indanedione
nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including its
thioketone body), a pyrazolone nucleus, an isooxazolinone nucleus,
an oxazolinone nucleus, a 1-indanone nucleus, a furanone nucleus,
an oxyindole nucleus, an imidazolidone nucleus, a
1,2,3,6-tetrahydropyridine- -2,6-dione nucleus, a
benzothiophene-3-one nucleus, an oxobenzothiophene-3-one nucleus, a
dioxobenzothiophene-3-one nucleus, a coumaranone nucleus, a
2-thio-2,4-thiazolidinedione nucleus, a 2-thio-2,4-oxazolidinedione
nucleus, a 2-thio-2,5-thiazolidinedione nucleus or a
2,4-thiazolidinedione nucleus. And L is a group derived from one
nucleus or two to six linked nuclei, the nucleus or nuclei of which
are selected from the family consisting of aniline, benzene,
thiophene, pyrrole, furan, selenophene, naphthalene, anthracene,
pyridine, pyridazine, pyrimidine, azulene, carbazole,
arylenevinylene, aryleneethynylene, arylenephenylene and
triarylamine (the arylene or aryl moiety of which is a group
derived from benzene, thiophene, pyrrole, furan, selenophene,
imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
triazine, indole, indazole, purine, thiazoline, thiazole,
thiadiazole, oxazoline, oxazole or oxadiazole). Such a nucleus or
nuclei may further be combined with an oxygen, nitrogen, sulfur or
methylene linkage.
[0176] Examples of a compound represented by formula (I) are
illustrated below, but it should be understood that these examples
are not to be construed as limiting the scope of the invention in
any way. 4950515253545556575859606162636465666768
[0177] Syntheses of some of the present compounds represented by
formula (I) are illustrated below.
[0178] Although various methods can be employed for synthesizing
compounds represented by formula (I), the case of the method in
which one aryl group of an arylamine compound is formylated and
then made to react with an active methylene compound in the
presence of a base is taken for illustration.
SYNTHESIS EXAMPLE 1
[0179] Synthesis of Compound (D-1) exemplified hereinbefore: 69
[0180] In 50 ml of ethanol, 2.7 g of
4-(N,N-diphenylamino)-benzaldehyde and 2.2 g of
5-phenylindane-1,3-dione were dissolved. Thereto, 1.0 g of
piperidine was added, and heated under reflux for 3 hours. The
resulting reaction solution was allowed to stand at room
temperature, and crystals separated out during the standing. The
crude crystals obtained was purified by column chromatography on
silica gel, and then recrystallized from an ethanol-chloroform
mixture to yield the desired product Compound (D-1). The product
showed the absorption maximum .lambda.max at 493 nm
(ClCH.sub.2CH.sub.2Cl) and the melting point at 178-181.degree.
C.
SYNTHESIS EXAMPLE 2
[0181] The desired Compound (D-2) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 512 nm and the melting point at
254-255.degree. C.
SYNTHESIS EXAMPLE 3
[0182] The desired Compound (D-5) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 468 nm.
SYNTHESIS EXAMPLE 4
[0183] The desired Compound (D-17) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 484 nm.
SYNTHESIS EXAMPLE 5
[0184] The desired Compound (D-22) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 469 nm.
SYNTHESIS EXAMPLE 6
[0185] The desired Compound (D-23) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 471 nm.
SYNTHESIS EXAMPLE 7
[0186] The desired Compound (D-51) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 492 nm.
SYNTHESIS EXAMPLE 8
[0187] The desired Compound (D-52) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 495 nm.
SYNTHESIS EXAMPLE 9
[0188] The desired Compound (D-53) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 507 nm.
SYNTHESIS EXAMPLE 10
[0189] The desired Compound (D-56) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 426 nm.
SYNTHESIS EXAMPLE 11
[0190] The desired Compound (D-57) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 527 nm.
SYNTHESIS EXAMPLE 12
[0191] The desired Compound (D-58) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 432 nm.
SYNTHESIS EXAMPLE 13
[0192] The desired Compound (D-59) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 451 nm.
SYNTHESIS EXAMPLE 14
[0193] The desired Compound (D-60) was synthesized using the same
method as in Synthesis Example 1. The synthesis product showed the
absorption maximum .lambda.max at 428 nm.
[0194] Then, the electroluminescent (EL) device comprising an
arylamine compound according to the invention (hereinafter referred
to as the present compound) is illustrated below.
SYNTHESIS EXAMPLE 15
[0195] The desired Compound (E-2) was synthesized in accordance
with the following reaction scheme: 70
[0196] In 50 ml of ethanol, 2.3 g of Intermediate A and 0.8 g of
Intermediate B were dissolved, and heated under reflux for 6 hours.
The reaction solution was allowed to stand at room temperature, and
thereby crystals were precipitated therefrom. These crude crystals
were filtered off, and purified by chromatography on silica gel.
Further, they were recrystallized from an ethanol-chloroform
mixture to yield the desired product, or Compound (E-2).
[0197] Then, the electroluminescent (EL) device comprising an amine
compound according to the invention (which is also referred to as
the present compound) is illustrated below.
[0198] The organic layers of an EL device comprising the present
compound have no particular restrictions as to the formation
method. Various methods, such as a resistance heating-utilized
vapor deposition method, an electron-beam heating method, a
sputtering method, a molecular lamination method, a coating method
and an ink jet method can be adopted. In particular, the resistance
heating-utilized vapor deposition method and the coating method are
favorable methods from the viewpoints of the characteristics
imparted to the device and the efficiency in producing the
device.
[0199] The present luminescent device is a device having a
luminescent layer or two or more thin layers of organic compounds,
including a luminescent layer, between a pair of electrodes, an
anode and a cathode. The thin layers the device may have in
addition to the luminescent layer are, e.g., a hole injection
layer, a hole transfer layer, an electron injection layer, an
electron transfer layer and a protective layer. The aforementioned
layers each may have another function also. For forming each layer,
various materials can be employed.
[0200] The anode supplies holes to a hole injection layer, a hole
transfer layer and a luminescent layer. As a material for the
anode, metals, alloys, metal oxides, electrically conductive
materials and mixtures thereof, preferably materials having a work
function of at least 4 eV, can be used. Examples of such materials
include conductive metal oxides, such as tin oxide, zinc oxide,
indium oxide and indium tin oxide (ITO), metals such as gold,
silver, chromium and nickel, mixtures or laminates of those metals
and conductive metal oxides, inorganic conductive materials such as
copper iodide and copper sulfide, organic conductive materials such
as polyaniline, polylthiophene and polypyrrole, and laminates of
those materials and ITO. Of the materials recited above, the
conductive metal oxides are favored over the others. In particular,
ITO is used to advantage from the viewpoint of productivity,
conductivity and transparency. The suitable thickness of the anode,
though can be selected depending on the anode material, is
generally from 10 nm to 5 .mu.m, preferably 50 nm to 1 .mu.m,
particularly preferably 100 nm to 500 nm.
[0201] The anode has on a soda lime glass, alkali-free glass or
transparent resin substrate an anode material formed into a layer.
In a case of using a glass substrate, alkali-free glass is
preferred from the viewpoint of reduction in ions eluted from the
glass. When soda glass is used as the substrate, it is desirable
that the barrier coat, such as silica, be provided on the glass.
The thickness of the substrate has no particular limitation as long
as the substrate can ensure mechanical strength for the anode. For
instance, the suitable thickness of a glass substrate is generally
at least 0.2 mm, preferably at least 0.7 mm. The methods suitable
for making the anode vary with the material used. In the case of
ITO, for example, the film formation can be carried out using an
electron-beam heating method, a sputtering method, a resistance
heating-utilized vapor deposition method, a chemical reaction
method (e.g., sol-gel method) or the method of coating a dispersion
of indium tin oxide. Washing and other treatments for the anode
enable the device to get a reduction in operating potential and
improve in light-emitting efficiency. In the case of an anode using
ITO, it is effective for the anode to receive UV-ozone treatment or
plasma treatment.
[0202] The cathode supplies electrons to an electron injection
layer, an electron transfer layer and a luminescent layer. In
selecting the cathode, the adhesiveness to the electron injection,
electron transfer or luminescent layer adjacent to the cathode,
ionization potential and the stability are taken into
consideration. As a material for the cathode, metals, alloys, metal
halides, metal oxides, electrically conductive materials and
mixtures thereof can be employed. Examples of such materials
include alkali metals (e.g., Li, Na, K) and the fluorides thereof,
alkaline earth metals (e.g., Mg, Ca) and the fluorides thereof,
gold, silver, lead, aluminum, Na--K alloy or the mixture thereof,
Li--Al alloy or mixture, Mg--Ag alloy or mixture, and rare earth
metals (e.g., In, Yb). Of these materials, the materials having a
work function of at most 4 eV are favored over the others. In
particular, aluminum, Li--Al alloy or mixture, and Mg--Ag alloy or
mixture are used to advantage. The cathode structure may be a
single-layer of the compound or mixture as recited above or a
laminate of the compounds and/or mixtures as recited above. The
suitable thickness of the cathode, though can be selected depending
on the cathode material, is generally from 10 nm to 5 .mu.m,
preferably 50 nm to 1 .mu.m, particularly preferably 100 nm to 1
.mu.m. Informing the cathode, various known methods, such as an
electron-beam heating method, a sputtering method, a resistance
heating-utilized vapor deposition method and a coating method, can
be adopted. The metals as recited above may be evaporated
independently, or two or more thereof may be evaporated
simultaneously. Further, it is possible to evaporate a plurality of
metals at the same time to form an alloy electrode, or to evaporate
the previously prepared alloy. It is advantageous to the
luminescent device that both anode and cathode have low sheet
resistance, specifically several hundreds .OMEGA./.quadrature. at
the highest.
[0203] The material usable for a luminescent layer is a material
capable of forming a layer which can function so as to receive both
hole injection from the anode, the hole injection layer or the hole
transfer layer and electron injection from the cathode, the
electron injection layer or the electron transfer layer when the
electric field is applied thereto, permit the charges injected
therein to move and enable the emission of light by providing a
place for recombining the holes and the electrons. As the material
as defined above, the present amine compounds can be contained in
the luminescent layer. In addition, other materials hitherto known
to be luminescent, such as benzoxazole derivatives, benzimidazole
derivatives, benzothiazole derivatives, styrylbenzene derivatives,
polyphenyl derivatives, diphenylbutadiene derivatives,
tetraphenylbutadiene derivatives, naphthalimide derivatives,
coumarin derivatives, perylene derivatives, perinone derivatives,
oxadiazole derivatives, aldazine derivatives, pyraridine
derivatives, cyclopentadiene derivatives, bisstyrylanthracene
derivatives, quinacridone derivatives, pyrrolopyridine derivatives,
thiadiazolopyridine derivatives, styrylamine derivatives, aromatic
dimethylidyne derivatives, various metal complexes represented by
metal or rare earth complexes of 8-quinolinol derivatives, and
polymeric compounds such as polythiophene, polyphenylene and
polyphenylenevinylene, may also be used in the luminescent layer.
Although the luminescent layer has no particular restrictions as to
the thickness, the suitable thickness thereof is generally from 1
nm to 5 .mu.m, preferably 5 nm to 1 .mu.m, particularly preferably
10 nm to 500 nm.
[0204] As to the method of forming the luminescent layer, there is
no particular restrictions, but various methods including a
resistance heating-utilized vapor deposition method, an
electron-beam heating method, a sputtering method, a molecular
lamination method, a coating method (e.g., a spin coating, cast
coating or dip coating method), an ink jet method and an LB method
can be adopted. Of these methods, resistance heating-utilized vapor
deposition and coating methods are favored over the others.
[0205] The materials for the hole injection layer and the hole
transfer layer may be any materials so long as they have any one of
the functions as an injector of the holes from the anode, a
transferor of holes and a barrier against electrons injected from
the cathode. Examples of materials hitherto known to have one of
such functions include carbazole derivatives, triazole derivatives,
oxazole derivatives, oxadiazole derivatives, imidazole derivatives,
polyarylalkane derivatives, pyrazoline derivatives, pyrazolone
derivatives, phenylenediamine derivatives, arylamine derivatives,
amino-substituted chalcone derivatives, styrylanthracene
derivatives, fluorenone derivatives, hydrazone derivatives,
stilbene derivatives, silazane derivatives, aromatic tertiary amine
compounds, styrylamine compounds, aromatic dimethylidyne compounds,
porphyrin compounds, polysilane compounds, and conductive polymers
or oligomers, such as poly(N-vinylcarbazole) derivatives, aniline
copolymers and thiophene oligomers or polythiophene. The thickness
of the hole injection layer and the hole transfer layer each,
though it has no particular limitation, is generally from 1 nm to 5
.mu.m, preferably 5 nm to 1 .mu.m, particularly preferably 10 nm to
500 nm. Each of the hole injection layer and the hole transfer
layer may have a single-layer structure constituted of one or more
of the materials recited above or a multiple-layer structure made
up of at least two layers having the same composition or different
compositions.
[0206] As a method of forming a hole injection layer and a hole
transfer layer, a vacuum evaporation method, an LB method, an ink
jet method and a method of coating a compound capable of injecting
or transferring holes in the form of a solution or dispersion in an
appropriate solvent (using, e.g., a spin coating, cast coating or
dip coating method) can be adopted. In the case of a coating
method, the compound can be dissolved or dispersed in the presence
of a resin component (binder polymer). Examples of such a resin
component include polyvinyl chloride, polycarbonate, polystyrene,
polymethyl methacrylate, polybutyl methacrylate, polyester,
polysulfone, polyphenylene oxide, pqlybutadiene,
poly(N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy
resin, polyamide, ethyl cellulose, polyvinyl acetate, ABS resin,
polyurethane, melamine resin, unsaturated polyester resin, alkyd
resin, epoxy resin and silicone resin.
[0207] The materials for the electron injection layer and the
electron transfer layer may be any materials so long as they have
any one of the functions as an injector of the electrons from the
cathode, a transferor of electrons and a barrier against holes
injected from the anode. Examples of compounds known to have such a
function include triazole derivatives, oxazole derivatives,
oxadiazole derivatives, fluorenone derivatives,
anthraquinodimethane derivatives, anthrone derivatives,
diphenylquinone derivatives, thiopyran dioxide derivatives,
carbodimide derivatives, fluorenylidenemethane derivatives,
distyrylpyrazine derivatives, heterocyclic tetracarboxylic acid
anhydrides such as naphthaleneperylene, phthalocyanine derivatives,
and various metal complexes represented by metal complexes of
B-quinolinol derivatives, metallophthalocyanine and metal complexes
containing benzoxazole or benzothiazole ligands. The thickness of
the electron injection layer and the electron transfer layer each,
though it has no particular limitation, is generally from 1 nm to 5
.mu.m, preferably 5 nm to 1 .mu.m, particularly preferably 10 nm to
500 nm. Each of the electron injection layer and the electron
transfer layer may have a single-layer structure constituted of one
or more the compounds as recited above, or a multiple-layer
structure made up of at least two layers having the same
composition or different compositions.
[0208] As a method of forming the electron injection layer and the
electron transfer layer, a vacuum evaporation method, an LB method,
an ink jet method and a method of coating the compound(s) capable
of injecting or transferring electrons in the form of a solution or
dispersion in an appropriate solvent (using, e.g., a spin coating,
cast coating or dip coating method) can be adopted. In a case of
adopting the coating method, the electron-injecting or transferring
compounds can be dissolved or dispersed in the presence of a resin
component. Examples of a resin component usable therein include the
same resins as employed for the hole injection and transfer
layers.
[0209] The materials for a protective layer may be any substances
so long as they have a function capable of inhibiting the invasion
of a device deterioration promoter, such as moisture or oxygen,
into the device. Examples of such a substance include metals, such
as In, Sn, Pb, Au, Cu, Ag, Al, Ti and Ni; metal oxides, such as
MgO, SiO, SiO.sub.2, Al.sub.2O.sub.3, GeO, NiO, CaO, BaO,
Fe.sub.2O.sub.3, Y.sub.2O.sub.3 and TiO.sub.2; metal fluorides,
such as MgF.sub.2, LiF, AlF.sub.3 and CaF.sub.2; polyethylene,
polypropylene, polymethyl methacrylate, polyimide, polyurea,
polytetrafluoroethylene, polychlorotrifluoroethylene- ,
polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene
and dichlorodifluoroethylene, copolymers prepared by polymerizing a
mixture of tetrafluoroethylene and at least one comonomer, and
fluorine-containing copolymers having cyclic structures on the main
chain; a water-absorbing substance having a water absorption rate
of at least 1%; and a moistureproof substance having a water
absorptivity of at most 0.1%.
[0210] The protective layer also has no particular restriction as
to the formation method, but any of a vacuum evaporation method, a
sputtering method, a reactive sputtering method, a molecular beam
epitaxy (MBE) method, a cluster ion beam method, an ion plating
method, a plasma polymerization method (high frequency excitation
ion plating method), a plasma chemical vapor deposition (CVD)
method, a laser CVD method, a heat CVD method, a gas source CVD
method, a coating method and an ink jet method can be adopted for
the formation thereof.
[0211] The present invention will now be illustrated in more detail
by reference to the following examples. However, the invention
should not be construed as being limited to these examples.
EXAMPEL 1
[0212] A transparent substrate having indium tin oxide (ITO) formed
into a 150 nm-thick layer on a glass substrate measuring 25
mm.times.25 mm.times.0.7 mm in size (produced by Tokyo Sanyo Shinku
K.K.) was etched and cleaned. Onto this substrate kept at room
temperature, an about 40 nm-thick
N,N'-bis(3-methylphenyl)-N,N'-diphenylbenzidine (TPD) film, an
about 40 nm-thick film of a compound selected from the compounds
set forth in Table 1 and an about 20 nm-thick tris
(8-hydroxyquinolinato) aluminum (Alq) film were evaporated in that
order under a vacuum of 10.sup.-3 to 10.sup.-4 Pa. On the organic
thin film lamination thus formed, a patterned mask (for adjusting
each emission area to 5 mm.times.5 mm) was set and further, inside
the vacuum evaporator, Mg and Ag were deposited simultaneously in a
Mg/Ag ratio of 10/1 to form a metallic film having a thickness of
250 nm, followed by deposition of a 300 nm-thick Ag film.
[0213] The thus produced organic luminescent device was made to
luminesce by applying thereto a DC constant voltage by means of a
source measure unit, Model 2400, made by Toyo Technica Co., Ltd.
The luminance and wavelength of the luminescence obtained were
measured with a luminometer BM-8 made by Topcon Co. and a spectrum
analyzer PMA-11 made by Hamamatsu Photonics Co. respectively. The
measurement results are shown in Table 1.
1TABLE 1 Driving Luminescent CIE chromaticity Device Luminance
potential wavelength coordinates No. Compound (cd/m.sup.2) (V)
.lambda.max (nm) (x, y) Dark spots 101 Comparative 210 14 600
(0.55, 0.45) X Compound A 102 Comparative 100 14 645 (0.62, 0.40) X
Compound B 103 Comparative 500 12 546 (0.45, 0.51) .DELTA. Compound
C 104 Comparative 800 12 612 (0.57, 0.41) .largecircle. Compound D
105 Present Compound 1300 12 614 (0.61, 0.38) .circleincircle. D-1
106 Present Compound 1200 14 648 (0.65, 0.34) .circleincircle. D-2
107 Present Compound 1100 13 646 (0.62, 0.37) .circleincircle. D-17
108 Present Compound 2700 12 610 (0.60, 0.40) .circleincircle. D-59
109 Present Compound 8500 12 536 (0.35, 0.58) .circleincircle. D-58
The symbols in Table 1 signify the following: .circleincircle.: No
dark spots can be confirmed by visual observation. .largecircle.:
There are few dark spots. .DELTA.: There are many dark spots. X:
There are a great many dark spots.
[0214] The structural formulae of Comparative Compounds used are as
follows: 71
[0215] As can be seen from the results set forth in Table 1, the
luminescent devices having luminescent layers made up of the
present compounds alone gave off luminescence of high luminance at
various wavelengths. This indicates that the present compounds are
useful as a luminescent material enabling the planar luminescence
of even quality. Moreover, the present compounds were found to
ensure excellent durability. In particular, when the luminescent
layer was formed using the present compound corresponding to the
compound having a substituent group or a condensed ring on the
1,3-indandione nucleus of Comparative Compound D, which is
described as an electron transferring material in JP-A-8-97465, the
present compounds of such structures sharpened the tone and shifted
the luminescence wavelength to the longer side to ensure high color
purity in the luminescence, and further showed excellent
durability. In addition, it was demonstrated that the present
compounds having 3-phenyl-1-indanone as their respective acidic
nuclei enabled the luminescence of particularly high luminance in
the orange to yellow region.
EXAMPLE 2
[0216] After etching and cleaning an ITO substrate in the same
manner as in Example 1, a TPD film having a thickness of about 40
nm was evaporated onto the ITO substrate, and further thereonto a
compound selected from the compounds set forth in Table 2 and Alq
(tris(8-hydroxyquinolinato)alu- minum) were evaporated
simultaneously at evaporation speeds of 0.04 .ANG./sec and 4
.ANG./sec respectively to form a film of about 60 nm. And then, a
cathode was deposited in the same manner as in Example 1. The thus
made luminescent devices were evaluated by the same method as in
Example 1. The evaluation results obtained are shown in Table
2.
2TABLE 2 CIE Luminescent chromaticity Device Luminance Driving
wavelength coordinates No. Compound (cd/m.sup.2) potential (V)
.lambda.max (nm) (x, y) 201 Comparative 250 15 605 (0.51, 0.48)
Compound A 202 Comparative 150 17 635 (0.64, 0.33) Compound B 203
Comparative 600 16 600 (0.53, 0.48) Compound C 204 Comparative 700
16 605 (0.53, 0.44) Compound D 205 Present 900 16 625 (0.60, 0.40)
Compound D-1 206 Present 900 16 638 (0.61, 0.37) Compound D-2 207
Present 800 16 630 (0.60, 0.39) Compound D-17
[0217] As can be seen from the results shown in Table 2, the use of
the present compounds as doping dyes enabled the luminescence of
high luminance and the production of planar luminescent materials
of even quality. Further, it was found that the luminescent
materials utilizing the present compounds as doping dyes had
excellent durability.
EXAMPLE 3
[0218] On the ITO substrate etched and cleaned in the same manner
as in Example 1, a solution containing 40 mg of
poly(N-vinylcarbazole), 12 mg of
2-(4-biphenylyl)-5-(4-tertbutylphenyl)-1,3,4-oxadiazole (PBD) and
0.5 mg of a compound selected from the compounds set forth in Table
3 in 3 ml of 1,2-dichloroethane was spin-coated. The thickness of
the organic thin film thus formed was about 120 nm. On the organic
thin film, a cathode was formed in the same manner as in Example 1.
The thus made luminescent devices were evaluated by the same method
as in Example 1. The results obtained are shown in Table 3.
3TABLE 3 CIE Driving Luminescent chromaticity Device Luminance
potential wavelength coordinates No. Compound (cd/m.sup.2) (V)
.lambda.max (nm) (x, y) 301 Comparative 220 17 600 (0.53, 0.46)
Compound A 302 Comparative 120 17 645 (0.62, 0.37) Compound B 303
Comparative 300 16 580 (0.51, 0.48) Compound C 304 Comparative 350
16 612 (0.55, 0.43) Compound D 305 Present 550 17 614 (0.60, 0.39)
Compound D-1 306 Present 500 17 645 (0.62, 0.36) Compound D-2 307
Present 480 16 635 (0.61, 0.39) Compound D-17
[0219] As can be seen from the results shown in Table 3, the
devices using the present compounds enabled the luminescence of
high luminance under low driving voltage though they were made by
the coating method generally providing low luminance to luminescent
devices, compared with those using the comparative compounds.
EXAMPLE 4
[0220] Onto the ITO substrate etched and cleaned in the same manner
as in Example 1, a TPD film having a thickness of about 40 nm was
evaporated and then a film of the present Compound D-2 was
evaporated in a thickness of about 80 nm, followed by vacuum
deposition of the same cathode as in Example 1.
[0221] As to the result of examinations made in the same way as in
Example 1, the thus made device showed the luminance of 50
cd/m.sup.2 under the driving voltage of 15 V, and the red
luminescence having high color purity of (0.65, 0.34), expressed in
the CIE chromaticity coordinates (x, y), and its .lambda.max at 631
nm was observed. Thus, the present compound has proved to be useful
as an electron injecting and transfer agent besides acting as a
luminescent substance.
EXAMPLE 5
[0222] On the ITO substrate etched and cleaned in the same manner
as in Example 1, a solution containing 40 mg of
poly(N-vinylcarbazole), 12 mg of
2,5-BIS(1-naphthyl)-1,3,4-oxadiazole, 10 mg of
1,1,4,4-tetraphenylbuta- diene, 0.5 mg of DCM and 0.1 mg of the
present Compound D-1 in 3 ml of 1,2-dichloroethane was spin-coated.
Thereon, a cathode was vacuum-deposited in the same manner as in
Example 1.
[0223] The thus made device was examined for luminescent
characteristics by applying DC voltage between the ITO electrode as
anode and the Mg:Ag electrode as cathode. At the driving voltage of
15 V, the device gave off the white luminescence (luminance: 1300
cd/m.sup.2) of (x, y)=(0.35, 0.36) on the CIE chromaticity
coordinates. Thus, the present compound has proved to be effective
for white luminescence.
EXAMPEL 6
[0224] A transparent substrate having a 150 nm-thick ITO layer on a
glass base measuring 25 mm.times.25 mm.times.0.7 mm in size
(produced by Tokyo Sanyo Shinku K.K.) was etched and cleaned. Onto
this substrate kept at room temperature, an about 40 nm-thick
N,N'-bis(3-methylphenyl)-N,N'-diph- enylbenzidine (TPD) film, an
about 40 nm-thick film of a compound selected from the compounds
set forth in Table 4 and an about 20 nm-thick tris
(8-hydroxyquinolinato) aluminum (Alq) film were evaporated in that
order under a vacuum of 10.sup.-3 to 10.sup.-4 Pa. On the organic
thin film lamination thus formed, a patterned mask (for adjusting
each emission area to 5 mm.times.5 mm) was set and further, inside
the vacuum evaporator, Mg and Ag were deposited simultaneously in a
Mg/Ag ratio of 10/1 to form a metallic film having a thickness of
250 nm, followed by deposition of a 300 nm-thick Ag film.
[0225] The thus prepared organic luminescent device was made to
produce luminescence by applying thereto a DC constant voltage by
means of a source measure unit, Model 2400, made by Toyo Technica
Co., Ltd. The luminance and the wavelength of luminescence thus
generated were measured with a luminometer BM-8 made by Topcon Co.
and a spectrum analyzer PMA-11 made by Hamamatsu Photonics Co.
respectively, thereby evaluating characteristics in the early
stages. Further, the state of planar luminescence was observed
after each device was made to produce luminescence for 100 hours by
the operation at a constant current of 5 mA in an atmosphere of
nitrogen. Furthermore, the thermal storage stability was evaluated
by storing each device for 24 hours at 80.degree. C. in an
atmosphere of nitrogen, causing the device to produce luminescence
and then observing the state of its luminous surface. The
measurement results are shown in Table 4.
4TABLE 4 Dark spots CIE after Dark spots Operating Luminescent
chromaticity producing after 24-hour Device Luminance potential
wavelength coordinates luminescenc storage at No. Compound
(cd/m.sup.2) (V) .lambda.max (nm) (x, y) for 100 hours 80.degree.
C. 401 Comparative 500 12 546 (0.45, 0.51) X X Compound C 402
Comparative 800 12 612 (0.57, 0.41) .DELTA. X Compound D 403
Present 1200 14 645 (0.65, 0.34) .largecircle. .DELTA. Compound E-2
404 Present 1500 15 640 (0.64, 0.35) .largecircle. .DELTA. Compound
E-27 Comparative compounds C and D are the same as those used in
Example 1. The symbols in Table 4 signify the following:
.largecircle.: No dark spots can be found by visual observation.
.DELTA.: There are few dark spots. X: There are many dark spot.
[0226] The results shown in Table 4 indicate that the use of the
present compounds each as the only constituent of a luminescent
layer enabled the resultant luminescent device to acquire
satisfactory color purity (expressed in CIE chromaticity) and
produce luminescence of high luminance. Further, few black spots
were observed in the luminescent devices using the present
compounds even after the devices continued to luminesce for many
hours. This observation result proves that the present compounds
ensured excellent durability for the luminescent devices. In
addition, the luminescent devices prepared using the present
compounds exhibited excellent planar luminescence and thermal
storage stability.
EXAMPLE 7
[0227] Onto the ITO substrate etched and cleaned in the same manner
as in Example 6 was evaporated a TPD film having a thickness of
about 40 nm. Further thereonto, a compound selected from the
compounds set forth in Table 5 and
tris(8-hydroxyquinolinato)aluminum (Alq) were evaporated
simultaneously at evaporation speeds of 0.04 .ANG./sec and 4
.ANG./sec respectively to form a film of about 40 nm. Furthermore
thereonto was evaporated an Alq film having a thickness of about 20
nm, followed by evaporation of the same cathode as in Example 6.
The thus prepared EL devices were evaluated by the same method as
in Example 6. The evaluation results obtained are shown in Table
5.
5TABLE 5 Dark spots CIE after Luminescent chromaticity producing
Luminance Operating wavelength coordinates luminescenc Device No.
Compound (cd/m.sup.2) potential (V) .lambda.max (nm) (x, y) for 100
hours 501 Comparative 600 16 600 (0.53, 0.46) .DELTA. Compound C
502 Comparative 830 16 605 (0.53, 0.44) .DELTA. Compound D 503
Present 950 16 635 (0.61, 0.37) .largecircle. Compound E-2 504
Present 1060 16 630 (0.60, 0.38) .largecircle. Compound E-27
[0228] The comparative Compounds C and D are the same as those used
in Example 1.
[0229] As can be seen from the results shown in Table 5, the use of
the present compounds as dopants enabled the luminescence of high
luminance and the production of planar luminescent materials of
even quality. Further, it has proved that the luminescent materials
containing the present compounds as dopants had excellent
durability.
EXAMPLE 8
[0230] On the ITO substrate etched and cleaned in the same manner
as in Example 6 was spin-coated a solution containing 40 mg of
poly(N-vinylcarbazole), 12 mg of
2-(4-biphenylyl)-5-(4-tert-butylphenyl)-- 1,3,4-oxadiazole (PBD)
and 0.5 mg of a compound selected from the compounds set forth in
Table 6 in 3 ml of 1,2-dichloroethane. The thickness of the organic
thin film thus formed was about 120 nm. Onto the organic thin film,
a cathode was evaporated in the same manner as in Example 6. The
thus prepared EL devices were evaluated by the same method as in
Example 6. The results obtained are shown in Table 6.
6TABLE 6 CIE Luminescent chromaticity Device Luminance Operating
wavelength coordinates No. Compound (cd/m.sup.2) potential (V)
.lambda.max (nm) (x, y) 601 Comparative 300 16 580 (0.51, 0.48)
Compound C 602 Comparative 350 16 612 (0.55, 0.43) Compound D 605
Present 570 16 640 (0.62, 0.36) Compound E-2 606 Present 600 17 635
(0.61, 0.37) Compound E-27
[0231] The comparative Compounds C and D are the same as those used
in Example 1.
[0232] As can be seen from the results shown in Table 6, the
devices using the present compounds enabled the luminescence of
high luminance under low operating voltage though they were made by
the coating method generally providing low luminance to luminescent
devices, compared with those using the comparative compounds.
EXAMPLE 9
[0233] Onto the ITO substrate etched and cleaned in the same manner
as in Example 6, a film of the present Compound E-2 having a
thickness of about 60 nm was evaporated. Then, a Alq film having a
thickness of about 40 nm was evaporated thereonto. Further thereon,
the same cathode as in Example 6 was formed by vacuum
deposition.
[0234] The evaluation results of the thus made device are as
follows: The luminance under the operating voltage of 15 V was 550
cd/m.sup.2, and the red luminescence having high color purity of
(0.63, 0.35), expressed in the CIE chromaticity coordinates (x, y),
and its .lambda.max at 640 nm was observed. Thus, the present
compound has proved to be useful as an electron injection and
transfer agent besides acting as a luminescent substance.
EXAMPLE 10
[0235] Onto the ITO glass substrate etched and cleaned in the same
manner as in Example 6, a
N,N'-bis(1-naphthyl)-N,N'-diphenylbenzidine (NPD) film having a
thickness of about 40 nm, a Compound D-2 film having a thickness of
about 20 nm, a Bathocuproine film having a thickness of about 10 nm
and an Alq film having a thickness of about 30 nm were evaporated
in that order. Further thereon, the same cathode as in Example 6
was formed by vacuum deposition.
[0236] The evaluation results of the thus made device are as
follows: The luminance under the operating voltage of 14 V was 1520
cd/m.sup.2, and the red luminescence having high color purity of
(0.63, 0.35), expressed in the CIE chromaticity coordinates (x, y),
and its .lambda.max at 643 nm was observed.
EXAMPLE 11
[0237] On the ITO glass substrate etched and cleaned in the same
manner as in Example 6, a solution containing 40 mg of
poly(N-vinylcarbazole), 12 mg of
2,5-bis(1-naphthyl)-1,3,4-oxadiazole, 10 mg of
1,1,4,4-tetraphenylbutadiene and 0.1 mg of the present Compound D-2
in 3 ml of 1,2-dichloroethane was spin-coated. Thereon, a cathode
was vacuum-deposited in the same manner as in Example 1.
[0238] The thus made device was examined for luminescent
characteristics by applying thereto a DC voltage while using the
ITO electrode as anode and the Mg:Ag electrode as cathode. At the
operating voltage of 15 V, the device gave off the white
luminescence (luminance: 1200 cd/m.sup.2) of (x, y)=(0.36, 0.35) on
the CIE chromaticity coordinates. Thus, the present compound has
proved to be effective for white luminescence.
Advantages of the Invention
[0239] When each of the particular amine compounds represented by
formula (I) according to the present invention forms one
constituent film of an EL device by themselves, the constituent
film enables the EL device to exhibit luminescence of high
luminance, especially red electroluminescence of high luminance and
high color purity, compared with the films of conventional
luminescent dyes, and can ensure excellent quality and high
durability for planar luminescent devices. Further, the use of the
present amine compound in an EL device of non-dope type enables the
production of devices of almost even quality to carry an advantage
of reducing the production cost. Moreover, even when the present
organic EL devices are made by a coating method known to generally
provide devices of low luminance, they can have excellent
luminescent characteristics.
* * * * *