U.S. patent application number 09/017872 was filed with the patent office on 2001-08-23 for fluorescent materials and their use.
Invention is credited to DENO, TAKASHI, DEVLIN, BRIAN GERRARD, KODAMA, KUNIHIKO, KUNIMOTO, KAZUHIKO, OTANI, JUNJI.
Application Number | 20010016269 09/017872 |
Document ID | / |
Family ID | 27514430 |
Filed Date | 2001-08-23 |
United States Patent
Application |
20010016269 |
Kind Code |
A1 |
OTANI, JUNJI ; et
al. |
August 23, 2001 |
FLUORESCENT MATERIALS AND THEIR USE
Abstract
A composition comprising (a) an effective amount of a guest
chromophore embedded in a matrix of a host chromophore, or (b) a
host chromophore and an effective amount of a guest chromophore
both embedded in a polymer matrix, wherein the absorption spectrum
of the guest chromophore overlaps with the fluorescence emission
spectrum of the host chromophore, and wherein the host chromophore
is selected from the group consisting of benzo [4,5] imidazo
[2,1-a] isoindol-11-ones.
Inventors: |
OTANI, JUNJI; (HYOGO,
JP) ; KUNIMOTO, KAZUHIKO; (OSAKA, JP) ; DENO,
TAKASHI; (HYOGO, JP) ; DEVLIN, BRIAN GERRARD;
(HYOGO, JP) ; KODAMA, KUNIHIKO; (HYOGO,
JP) |
Correspondence
Address: |
JOANN L VILLAMIZAR
PATENT DEPARTMENT
CIBA SPECIALTY CHEMICALS CORPORATION
540 WHITE PLAINS ROAD
TARRYTOWN
NY
10591
|
Family ID: |
27514430 |
Appl. No.: |
09/017872 |
Filed: |
February 3, 1998 |
Current U.S.
Class: |
428/690 ;
252/301.16; 252/301.34; 252/301.35; 257/102; 313/502; 313/504;
313/506; 428/917 |
Current CPC
Class: |
C07D 487/04 20130101;
C09B 67/0033 20130101; C09B 57/12 20130101; Y10S 428/917 20130101;
C09B 69/109 20130101; C09K 11/06 20130101 |
Class at
Publication: |
428/690 ;
428/917; 313/502; 313/504; 313/506; 257/102; 252/301.16;
252/301.34; 252/301.35 |
International
Class: |
H05B 033/14; C09K
011/06 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 3, 1997 |
EP |
97810049.3 |
Feb 3, 1997 |
EP |
97810050.1 |
Feb 3, 1997 |
EP |
97810051.9 |
Feb 4, 1997 |
EP |
97810054.3 |
Feb 4, 1997 |
EP |
97810055.0 |
Claims
1. A composition comprising (a) an effective amount of a guest
chromophore embedded in a matrix of a host chromophore, or (b) a
host chromophore and an effective amount of a guest chromophore
both embedded in a polymer matrix, wherein the absorption spectrum
of the guest chromophore overlaps with the fluorescence emission
spectrum of the host chromophore, and wherein the host chromophore
is selected from the group consisting of benzo [4,5] imidazo
[2,1-a] isoindol-11-ones.
2. A composition according to claim 1, characterized in that (a)
the guest chromophore is homogeneously distributed within the
matrix of the host chromophore, or (b) the host chromophore and the
guest chromophore both are homogeneously distributed within the
polymer matrix.
3. A composition according to claim 1, characterized in that the
guest chromophore is selected from the group consisting of
quinacridones, perylenes, perinones, diketo- and
dithioketopyrrolopyrroles, rhodamines, coumarins, xanthens,
oxazines, oxazoles, cyanines, phthalocyanines, porphyrines, styryl
dyes, metal complexes and mixtures thereof.
4. A process for the preparation of a composition according to
claim 1, comprising a host chromophore and a guest chromophore and,
if desired, a polymer matrix, wherein the absorption spectrum of
the guest chromophore overlaps with the fluorescence emission
spectrum of the host chromophore, characterized in (a) selecting
the host chromophore from the group consisting of
benzo[4,5]imidazo[2,1-a] -isoindol-11-ones, (b) mixing the host
chromophore and an effective amount of at least one guest
chromophore, and optionally a polymer or polymerisable precursor,
in the presence of a solvent, and c) then precipitating the host
and guest chromophores, optionally in the presence the polymer of
step (b), or (d) precipitating the host and guest chromophores
during polymerization of the polymer precursor of step (b).
5. A polymerisable composition comprising polymerisable monomers or
prepolymers in admixture with a composition of claim 1 in the form
of a powder containing particles, or with host and guest
chromophores according to claim 1, preferably dissolved therein, or
both.
6. A composition comprising a carrier material with a high relief
image of a polymerized photoresist material, which contains a
composition of claim 1 in the form of a powder containing
particles, or host and guest chromophores according to claim 1, or
both, if desired dissolved and/or homogeneously distributed
therein.
7. A process for the preparation of fluorescent high relief images
on a carrier, characterized in irradiating under a mask or by laser
writing, the coated photopolymerisable composition according to
claim 5, preferably dried and removed of solvent, on the carrier,
developing the irradiated composition and finally removing the
non-irradiated parts.
8. Method for the use of the compositions according to claim 1 as
fluorescent materials.
9. A compound of the formula V, 14wherein at most three of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are H and at least one of
R.sub.13, R.sub.14, R,.sub.15 and R.sub.16 are a substituent
selected from the group of C.sub.1 to C.sub.18alkyl, C.sub.1 to
C.sub.18alkoxy, C.sub.1 to C.sub.18alkylthio, C.sub.1 to
C.sub.12alkoxy-polyC.sub.2 to C.sub.6oxyalkylene; unsubstituted or
with F, Cl, Br, --CN, C.sub.1 to C.sub.12alkyl, C.sub.1 to
C.sub.12alkoxy, C.sub.1 to C.sub.12alkylthio, or-NR.sub.2R.sub.22
substituted C.sub.5 to C.sub.8cycloalkyl, C.sub.5 to
C.sub.8cycloalkoxy, C.sub.5 to C.sub.8cycloalkylthio, C.sub.5 to
C.sub.8cycloalkyl-C.sub.1 to C.sub.4alkyl, C.sub.5 to
C.sub.8cycloalkyl-C.sub.1 to C.sub.4alkoxy, C.sub.5 to C.sub.8
cycloalkyl-C.sub.1 to C.sub.4alkylthio, phenyl, phenyloxy,
phenylthio, phenyl-C.sub.1 to C.sub.4alkyl, phenyl-C.sub.1 to
C.sub.4alkoxy, phenyl-C.sub.1 to C.sub.4alkylthio; or R.sub.13 and
R.sub.14 together, R.sub.15 and R.sub.16 together, or R.sub.13 and
R.sub.14 together and R.sub.15 and R.sub.16 together, or R.sub.14
and R.sub.15 together are selected from the groups
--CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd.CH--,
--CH.dbd.CR.sub.24-CR.sub.25.dbd.N-- -,
--CH.dbd.N-CR.sub.25.dbd.CH--, --CH.dbd.CR.sub.24-N.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd. N--, --N.dbd.CR.sub.24-N.dbd.CH--,
--CH.dbd.CH-O--, --CH.dbd.CH-S--, --CH.dbd.CH-NR.sub.23--; R.sub.17
and R.sub.20 independently from one another are H or have the
meaning of R.sub.18; one of R.sub.18 and R.sub.19 are H and the
other of R.sub.18 and R.sub.19 or both are a substituent selected
from the group of C.sub.1 to C.sub.18alkyl, C.sub.1 to
C.sub.18alkoxy, C.sub.1 to C.sub.18alkylthio, C.sub.1 to
C.sub.12alkoxy-polyC.sub.2 to C.sub.6-oxyalkylene; unsubstituted or
with F, Cl, Br, --CN, C.sub.1 to C.sub.12alkyl, C.sub.1 to
C.sub.12alkoxy, C.sub.1 to C.sub.12alkylthio, or
--NR.sub.21R.sub.22 substituted C.sub.5 to C.sub.8cycloalkyl,
C.sub.5 to C.sub.8cycloalkoxy, C.sub.5 to C.sub.8cycloalkylthio,
C.sub.5 to C.sub.8cycloalkyl-C.sub.1 to C.sub.4alkyl, C.sub.5 to
C.sub.8cycloalkyl-C.sub.1 to C.sub.4alkoxy, C.sub.5 to
C.sub.8cycloalkyl-C.sub.1 to C.sub.4alkylthio, phenyl, phenyloxy,
phenylthio, phenyl-C.sub.1 to C.sub.4alkyl, phenyl-C.sub.1 to
C.sub.4alkoxy, phenyl-C.sub.1 to C.sub.4alkylthio, phenyl-C.sub.2
to C.sub.12alkylidene, phenyl-C(O)--, phenyl-NR.sub.23-C(O)--,
phenyl-NR.sub.23-S(O).sub.2--, phenyl-S(O)--, phenyl-S(O).sub.2--,
phenyl-CO.sub.2--, phenyl-S(O)-O--, phenyl-SO.sub.3--,
phenyl-NR.sub.23--, or phenyl-CH.dbd.CH--; or R.sub.17 and R.sub.18
together, R.sub.19 and R.sub.20 together, or R.sub.17 and R.sub.18
together and R.sub.19 and R.sub.20 together, or R.sub.18 and
R.sub.19 together are selected from the groups
--CH.dbd.CR.sub.24-CR.sub.25.dbd.CH- --,
--N.dbd.CR.sub.24-CR.sub.25.dbd.CH--,
--CH.dbd.CR.sub.24-CR.sub.25.dbd- .N--,
--CH.dbd.N-CR.sub.25.dbd.CH--, --CH.dbd.CR.sub.24-N.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd.N--, --N.dbd.CR.sub.24-N.dbd.CH--,
--CH.dbd.CH-O--, --CH.dbd.CH-S--, --CH.dbd.CH-NR.sub.23--; R.sub.23
and R.sub.22 are independently from one another are C.sub.1 to
C.sub.20alkyl, phenyl, C.sub.1 to C.sub.12alkylphenyl, benzyl or
C.sub.1 to C.sub.12alkylbenzyl, or R.sub.21 and R.sub.22 together
mean tetramethylene, pentamethylene or
--CH.sub.2CH.sub.2-O-CH.sub.2CH.sub.2--- ; R.sub.23 is H C.sub.1 to
C.sub.4alkyl or benzyl; and R.sub.24 and R.sub.25 are independently
from one another H, C.sub.1 to C.sub.6alkyl, C.sub.1 to
C.sub.6alkoxy, C.sub.1 to C.sub.6alkylthio, or F, Cl or Br.
10. A compound according to claim 9, characterized in that it
corresponds to formula VI, 15wherein R.sub.17 and R.sub.20 are H,
and R.sub.18 and R.sub.19 or both are C.sub.1 to C.sub.18alkyl or
C.sub.1 to C.sub.18alkoxy, or R.sub.18 and R.sub.19 together mean
--CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--; or R.sub.17 and R.sub.18
together or R.sub.19 and R.sub.20 together, or R.sub.17 and
R.sub.18 together and R.sub.19 and R.sub.20 together mean
--CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--- , wherein R.sub.24 and
R.sub.25 are independently from one another H, F, Cl, C.sub.1 to
C.sub.8alkyl or C.sub.1 to C.sub.8alkoxy.
11. A compound of the formula VIa, 16wherein X.sub.1 is Cl or Br,
one of R'.sub.18 and R'.sub.19 or both are independently from one
another --COOH, or .alpha.- or .alpha.,.alpha. -branched C.sub.3 to
C.sub.20alkyl or Ra-C(O)--, wherein R.sub.a means C.sub.1 to
C.sub.20alkyl; or C.sub.5 to C.sub.8cycloalkyl, C.sub.5 to
C.sub.8cycloalkyl-CH.sub.2--, phenyl, benzyl, which are
unsubstituted or substituted with halogen, C.sub.1 to C.sub.12alkyl
or C.sub.1 to C.sub.12alkoxy, or one of R'.sub.18 and R'.sub.19 is
.alpha.- or .alpha.,.alpha.-branched C.sub.3 to C.sub.20alkyl or
Ra-C(O)--, wherein R.sub.a means C.sub.1 to C.sub.20alkyl; or
C.sub.5 to C.sub.8cycloalkyl, C.sub.5 to
C.sub.8cycloalkyl-CH.sub.2--, phenyl, benzyl, which are
unsubstituted or substituted with halogen, C.sub.1 to C.sub.12alkyl
or C.sub.1 to C.sub.12alkoxy, and the other of R'.sub.18 and
R'.sub.19 is linear C.sub.1 to C.sub.12alkyl.
12. Method for the use of compound V according to claim 9 as
organic emitting material in and for the preparation of
electroluminescence ("EL") devices.
13. Method for the use of compound VI according to claim 10 as
organic emitting material in and for the preparation of
electroluminescence ("EL") devices.
14. Method for the use of compound VIa according to claim 11 as
organic emitting material in and for the preparation of
electroluminescence ("EL") devices.
15. Method for the use of the compositions according to claim 1 as
organic emitting materials in and for the preparation of
electroluminescence ("EL") devices.
16. Electroluminescence device according to the method of claim
12.
17. Electroluminescence device according to the method of claim
13.
18. Electroluminescence device according to the method of claim
14.
19. Electroluminescence device according to the method of claim 15.
Description
[0001] The present invention relates to a composition comprising
(a) an effective amount of a guest chromophore embedded in a matrix
of a host chromophore, or (b) a host chromophore and an effective
amount of a guest chromophore both embedded in a polymer matrix,
wherein the absorption spectrum of the guest chromophore overlaps
with the fluorescence emission spectrum of the host chromophore,
and wherein the host chromophore is selected from the group
consisting of benzo [4,5] imidazo [2,1-a] isoindol-11-ones.
[0002] Further, the present invention relates to a process for the
preparation of this composition, a polymerisable composition
comprising this composition, a composition comprising a carrier
material with a high relief of a polymerized photoresist material
containing this composition, a process for the preparation of
fluorescent high relief images on a carrier, the use of the
compositions as fluorescent materials, especially in
electroluminescent devices, and novel non-functionalized
benzo[4,5]imidazo[2,1-a]isoindol-11-one derivatives.
[0003] Combinations comprising host chromophores with guest
chromophores dissolved therein to generate materials with enhanced
fluorescence and large differences between absorption maximum and
emission maximum are highly desired materials that possess a wide
range of potential and actual technical applications. The large
difference between the absorption (excitation) maximum and the
emission maximum is due to the occurrence of resonant energy
transfer between the respective host and guest chromophores.
[0004] The possibility of energy transfer between chromophores that
possess an area of overlap of the absorption spectrum of a guest
chromophore with the fluorescence emission spectrum of a host is
known. For example, H. Port et al. describe in Z. Naturforsch.,
36a, pages 697 to 704 (1981) mixed crystals of fluorene doped with
dibenzofurane or benzindan with an enhanced fluorescence in the UV
region at temperatures below 100 K. However, the low temperature
fluorescence has no practical value and is only of scientific
interest.
[0005] C. W. Tang et al. disclose in J. Appl. Phys., 65, 3610 to
3616 (1989) a multilayered electroluminescent device with a light
emitting layer composed of 8-hydroxyquinoline aluminum, in which is
embedded a zone doped with a fluorescent molecule such as coumarin.
The device shows improved electroluminescence and an effective
Stoke's color shift which is dependent on the particular dopant.
The manufacture of the device is complicated and not readily
suitable for an industrial production.
[0006] J. M. Lang et al. describe in J. Phys. Chem. 97, pages 5058
to 5064 (1993) the combination of coumarin as host and rhodamine as
guest whereby both components are dissolved in polyacrylic acid,
but Lang's study demonstrates enhanced fluorescence only under high
pressure.
[0007] In WO 93/23492 are disclosed fluorescent microparticles with
an enhanced Stokes shift, which are composed of soluble and
fluorescent host and guest dyes absorbed or bonded to polymeric
microparticles. The material is used for the optical detection of
nucleic acids like DNA or RNA. Unfavorably, the solid state
fluorescence of these microparticles is poor.
[0008] U.S. Pat. No. 5,227,252 discloses a fluorescent composition
of 8-hydroxyquinoline aluminum as host and quinacridones as guest.
Similarly, JP-A-05 320 633 discloses a fluorescent composition of
8-hydroxyquinoline aluminum as host and diketopyrrolopyrroles as
guest. However, in both documents, the guests are insoluble
materials, they are dissolved mainly as microsized clusters. The
occurrence of microsized clusters is due to co-sublimation
processes being the means of preparation. The materials possess a
larger Stoke's shifts than would be anticipated by normal single
component fluorescent materials, and are used for example as light
emitting materials in electroluminescent devices. The process for
their manufacture requires large expenditures on technical
equipment to ensure the careful control process conditions such as
vacuum and temperature, to achieve the desired mixed material. The
process is not convenient for large scale industrial
manufacture.
[0009] In EP-A-0 456 609 is disclosed a process for the preparation
of 1,2,3,4-tetrachlorobenzo[4,5] imidazo[2,1-a]isoindol-11-one and
its derivatives in the presence of selected solvents. These
compounds are pigments showing solid state fluorescence and
improved outdoor durability. It is also mentioned therein, that the
combination of 95% of the yellow 1,2,3,4-tetrachloro-benzo[4,5]
imidazo[2,1-a]isoindol-11-one with 5% of Indanthrone Blue generates
a green fluorescent pigment. Hence, such a system is a pigment
composite, wherein the new color generated is simply a sum of the
two component colors. The color is not created by virtue of the
occurrence of complex, molecular level, energy transfer processes
that require close interaction between the components of the
mixture.
[0010] F. W. Harris et.al. describe in ACS Symp. Ser. 132, 39
(1980) the compound 1,2,3,4-tetraphenyl-benzo [4,5] imidazo [2,1-a]
isoindol-11-one as a model material, as a part of their
investigations into phenylated polyimidazopyrrolones for potential
use in aerospace applications. However, no reference to its
fluorescence behavior is made.
[0011] Hence, the object of the invention on hand was to find a
fluorescent composition, which does not show the above mentioned
disadvantages, preferably a composition should be provided
which
[0012] has a greatly enhanced and intense fluorescence
emission,
[0013] shows an intense solid state fluorescence, wherein the
emission spectrum is preferably in the visible region of the
electromagnetic spectrum,
[0014] is excitable using wavelengths in both the UV and visible
regions,
[0015] shows a very excellent photostability and outdoor
durability,
[0016] shows a wide range of emission spectra through selection of
suited guest molecules (color tuning),
[0017] has a high thermal stability,
[0018] is easily prepared, i.e. by a (co-)precipitation
process,
[0019] can be used for the preparation of electroluminescence
devices,
[0020] if the host chromophore is selected from the group
consisting of benzo[4,5]imidazo[2,1-a]isoindol-11-ones, which means
derivatives of benzo[4,5]imidazo[2,1-a]isoindol-11-one as the
fundamental substance.
[0021] In addition, the enhancement factor for the present
compositions preferably should be all positive and should be at
least 1.3, more preferably at least 2 and most preferably at least
5. The term "enhancement factor" as used herein, is defined as the
increased or decreased factor, in terms of peak height emission
intensities of a solid-state powder comprising of host and guest
fluorescent moieties compared to an identical powder that does not
contain any fluorescent guest moieties. Comparisons are considered
real, for as long as the excitation radiation wavelengths are
identical. In general, the emission wavelengths of host/guest
material occur at longer wavelengths (lower energy) as compared to
an identical material with no guest component.
[0022] Accordingly, a composition was found comprising (a) an
effective amount of a guest chromophore embedded in a matrix of a
host chromophore, or (b) a host chromophore and an effective amount
of a guest chromophore both embedded in a polymer matrix, wherein
the absorption spectrum of the guest chromophore overlaps with the
fluorescence emission spectrum of the host chromophore, and wherein
the host chromophore is selected from the group consisting of
benzo[4,5]imidazo [2,1-a] isoindol-11-ones.
[0023] In addition, a process for the preparation of this
composition, a polymerizable composition comprising this
composition, a composition comprising a carrier material with a
high relief of a polymerized photoresist material containing this
composition, a process for the preparation of fluorescent high
relief images on a carrier, the use of the compositions as
fluorescent materials, esp. in electroluminescent devices, and
novel non-functionalized benzo[4,5]imidazo[2,1-a]isoindol-11- -one
derivatives were found, too.
[0024] A first embodiment of the present invention relates to a
composition comprising (a) an effective amount of a guest
chromophore embedded in a matrix of a host chromophore, or (b) a
host chromophore and an effective amount of a guest chromophore
both embedded in a polymer matrix, wherein the absorption spectrum
of the guest chromophore overlaps with the fluorescence emission
spectrum of the host chromophore, and wherein the host chromophore
is selected from the group consisting of benzo [4,5] imidazo
[2,1-a] isoindol-11-ones.
[0025] The host chromophore is selected from the group consisting
of derivatives of benzo[4,5]imidazo[2,1-a]isoindol-11-one and
benzo[4,5]imidazo[2,1-a]isoindol-11-one (hereinafter referred to as
benzoimidazoisoindolone(s)) itself. The compounds are preferably
derivatives that are soluble in an organic or aqueous solvent.
[0026] Under the aspects of the invention solubility of host
chromophores means preferably that at least 10 mg, more preferably
at least 50 mg and most preferably at least 100 mg of the
benzoimidazoisoindolone derivative are soluble in 1 liter of
solvent like dimethylformamide, at 20.degree. C. It is
self-evident, that the solubilities are higher at increasing
temperatures and depend on the choice of a solvent.
[0027] The benzoimidazoisoindolones may correspond to the formula I
1
[0028] wherein the neighboring carbon atoms of the benzene rings 1
and 2 are uncondensed or condensed with benzene rings,
heteroaromatic rings, aliphatic rings, or heteroaliphatic rings,
and wherein the benzene rings 1 or 2 or both, the condensed ring
moieties or all are unsubstituted or substituted with organic
groups and/or halogen atoms.
[0029] The groups forming a condensed ring are preferably selected
from the group consisting of bivalent residues of formulae
--CH.dbd.CH-CH.dbd.CH--, --CH.dbd.CH-N.dbd.CH--,
--CH.dbd.CH-CH.dbd.N--, --CH.dbd. N-CH.dbd.N--,
--CH.dbd.CH-NR.sub.1--, --CH.dbd.N-CH.sub.2--, --CH.dbd.CH-S--,
--CH.dbd.CH-O--, --(CH.sub.2).sub.3--, --(CH.sub.2).sub.4--,
--CH.sub.2-CH.sub.2-NR.sub.1-CH.sub.2--,
--CH.sub.2-CH.sub.2-CH.sub.2-NR.sub.1--,
--CH.sub.2-CH.sub.2-O-CH.sub.2--- ,
--CH.sub.2-CH.sub.2-CH.sub.2-O--, --CH.sub.2-CH.sub.2-S-CH.sub.2--,
--CH.sub.2-CH.sub.2-CH.sub.2-S--, --CH.sub.2-O-CH.sub.2--,
--CH.sub.2-CH.sub.2-O--, --CH.sub.2-S-CH.sub.2--, and
--CH.sub.2-CH.sub.2-S--, wherein R.sub.1 is H or an organic
substituent, and the bivalent residues are unsubstituted or
substituted with an organic group.
[0030] R.sub.1, as organic substituent, may be linear or branched
C.sub.1 to C.sub.20alkyl, C.sub.5 to C.sub.7cycloalkyl, benzyl or
R.sub.2-C(O)--, wherein R.sub.2 is C.sub.1 to C.sub.20alkyl, which
is unsubstituted or substituted with F, Cl or C.sub.1 to
C.sub.12alkoxy, or C.sub.5 to C.sub.7cycloalkyl, phenyl or benzyl,
which are is unsubstituted or substituted with F, Cl, C.sub.1 to
C.sub.12alkyl, or C.sub.1 to C.sub.12alkoxy.
[0031] Preferred examples for R.sub.1 are H, methyl, ethyl, propyl,
butyl, pentyl, hexyl, benzyl, methylbenzyl, dimethylbenzyl, acetyl,
propionyl, butyroyl, benzyl-C(O)--, phenyl-C(O)--, toluyl-C(O)--,
mono-, di- or tri-chloroacetyl, and mono-, di- or tri-fluoroacetyl,
mono- and dichlorophenyl-C(O)--.
[0032] The organic substituent may be selected from the group
consisting of halogen, --CN, --NO.sub.2, C.sub.1 to C.sub.18 alkyl,
C.sub.2 to C.sub.18alkenyl, C.sub.2 to C.sub.18alkinyl, C.sub.1 to
C.sub.18 hydroxyalkyl, C.sub.1 to C.sub.18 halogenalkyl, C.sub.3 to
C.sub.12 cycloalkyl, C.sub.6 to C.sub.18 aryl, C.sub.5 to C.sub.17
heteroaryl, C.sub.3 to C.sub.12 cycloalkylalkyl, C.sub.6 to
C.sub.18 aralkyl, C.sub.5 to C.sub.17 heteroaralkyl, C.sub.1 to
C.sub.18 alkyloxy, C.sub.3 to C.sub.12 cycloalkyloxy, C.sub.6 to
C.sub.18 aryloxy, C.sub.5 to C.sub.17 heteroaryloxy, C.sub.3 to
C.sub.12 cycloalkylalkyloxy, C.sub.6 to C.sub.18 aralkyloxy,
C.sub.5 to C.sub.17 heteroaralkyloxy, C.sub.1 to C.sub.18
alkylthio, C.sub.3 to C.sub.12 cycloalkylthio, C.sub.6 to C.sub.18
arylthio, C.sub.5 to C.sub.17 heteroarylthio, C.sub.3 to C.sub.12
cycloalkylalkylthio, C.sub.6 to C.sub.18 aralkylthio, C.sub.5 to
C.sub.17 heteroaralkylthio, C.sub.1 to C.sub.18 alkyl-SO-- or
--SO.sub.2, C.sub.3 to C.sub.12 cycloalkyl-SO-- or --SO.sub.2,
C.sub.6 to C.sub.18aryl-SO-- or --SO.sub.2, C.sub.5 to C.sub.17
heteroaryl-SO-- or --SO.sub.2, C.sub.3 to C.sub.12
cycloalkylalkyl-SO-- or --SO.sub.2, C.sub.6 to C.sub.18
aralkyl-SO-- or --SO.sub.2, C.sub.1 to C.sub.18 alkyl-CO--, C.sub.3
to C.sub.12 cycloalkyl-CO--, C.sub.6 to C.sub.18aryl-CO--, C.sub.5
to C.sub.17 heteroaryl-CO--, C.sub.3 to C.sub.12
cycloalkylalkyl-CO--, C.sub.6 to C.sub.18 aralkyl-CO--, C.sub.5 to
C.sub.17 heteroaralkyl-CO--, --NR.sub.3R.sub.4, alkoxyalkyl with 2
to 20 carbon atoms, polyoxyalkylene-OR.sub.6,
--X-(R.sub.5).sub.k-C(O)-NR.su- b.3R.sub.4,
--X-(R.sub.5).sub.k-C(O)-OR.sub.6, --X-(R.sub.5).sub.k-SO.sub.-
2-OR.sub.6, --X-(R.sub.5).sub.k-SO.sub.2-NR.sub.3R.sub.4,
--NH-C(O)-R.sub.6 and --O-C(O)-R.sub.6,
[0033] wherein
[0034] R.sub.3 and R.sub.4 independently from one another mean H,
C.sub.1 to C.sub.20alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl,
C.sub.1 to C.sub.12alkylphenyl or C.sub.1 to C.sub.12alkylbenzyl,
or R.sub.3 and R.sub.4 together mean tetramethylene,
pentamethylene, or the groups
--CH.sub.2-CH.sub.2-O-CH.sub.2-CH.sub.2-- or
--CH.sub.2-CH.sub.2-NR.sub.3- -CH.sub.2-CH.sub.2--,
[0035] R.sub.5 is C.sub.1 to C.sub.12alkylene, phenylene or
benzylene,
[0036] R.sub.6 means H, C.sub.1 to C.sub.20alkyl, cyclopentyl,
cyclohexyl, phenyl, benzyl, C.sub.1 to C.sub.12alkylphenyl or
C.sub.1 to C.sub.12alkylbenzyl,
[0037] X is a direct bond, --O-- or S,
[0038] k is 0 or 1 and
[0039] and the salts of the acids.
[0040] Preferred salts are the alkaline metal and earth alkaline
metal salts, e.g. from Li, Na, K, Mg, Ca, Sr, Ba.
[0041] The cyclic aliphatic and aromatic residues (substituents for
the organic group) may be also substituted, for example with
halogen like F, Cl or Br, --CN, --NO.sub.2, C.sub.1 to
C.sub.18alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.6 to
C.sub.18aryl, C.sub.3 to C.sub.12cycloalkylalkyl, C.sub.6 to
C.sub.18aralkyl, C.sub.5 to C.sub.17heteroaralkyl, C.sub.1 to
C.sub.18 alkyloxy, C.sub.3 to C.sub.12 cycloalkyloxy, C.sub.6 to
C.sub.18 aryloxy.
[0042] In the context of the invention the alkyl substituent may be
linear or branched and contains preferably 1 to 12 C-atoms, more
preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms and
particularly preferred 1 to 4 C-atoms. Some examples are methyl,
ethyl, n- or i-propyl, n-, i- or t-butyl, and the isomers of
pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and
octadecyl.
[0043] In the context of the invention the halogen substituent may
be F, Cl, Br or I and is preferably For Cl.
[0044] In the context of the invention the alkenyl substituent may
be linear or branched and contains preferably 2 to 12 C-atoms, more
preferably 2 to 8 C-atoms, most preferably 2 to 6 C-atoms and
particularly preferred 2 to 4 C-atoms. Some examples are vinyl,
allyl, methylvinyl, but-1-ene-4-yl, but-2-ene-4-yl, but-3-ene-4-yl,
3-methyl-prop-1-ene-3-yl, and the isomers of pentenyl, hexenyl,
heptenyl, octenyl, nonenyl, decenyl, undeencyl, dodecenyl,
tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl
and octadecenyl.
[0045] In the context of the invention the alkinyl substituent may
be linear or branched and contains preferably 2 to 12 C-atoms, more
preferably 2 to 8 C-atoms, most preferably 2 to 6 C-atoms and
particularly preferred 2 to 4 C-atoms. Some examples are ethinyl,
crotonyl, methylethinyl, but-1-ine-4-yl, but-2-ine-4-yl,
but-3-ine-4-yl, 3-methyl-prop-1-in-3-yl, and the isomers of
pentinyl, hexinyl, heptinyl, octinyl, noninyl, decinyl, undecinyl,
dodecinyl, tridecinyl, tetradecinyl, pentadecinyl, hexadecinyl,
heptadecinyl and octadecinyl.
[0046] In the context of the invention the hydroxyalkyl substituent
may be linear or branched and contains preferably 1 to 12 C-atoms,
more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms and
particularly preferred 1 to 4 C-atoms. Some examples are
hydroxymethyl, hydroxyethyl, n- or i-hydroxypropyl, n-, i- or
t-hydroxybutyl, and the isomers of hydroxypentyl, hydroxyhexyl,
hydroxyheptyl, hydroxyoctyl, hydroxynonyl, hydroxydecyl,
hydroxyundecyl, hydroxydodecyl, hydroxytridecyl, hydroxytetradecyl,
hydroxypentadecyl, hydroxyhexadecyl, hydroxyheptadecyl and
hydroxyoctadecyl.
[0047] In the context of the invention the halogenalkyl substituent
may be linear or branched and contains preferably 1 to 12 C-atoms,
more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms and
particularly preferred 1 to 4 C-atoms. The halogen may be F, Cl, Br
or I, and is preferably F and Cl. Some examples are chloromethyl,
dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,
trifluoromethyl, chloroethyl, n- or i-chloropropyl, n-, i- or
t-chlorobutyl, perfluoroethyl and perfluorobutyl.
[0048] In the context of the invention the cycloalkyl substituent
contains preferably 4 to 8 and more preferred 5 to 7 ring carbon
atoms. Examples are cyclopropyl, cyclobutyl, cyclopentyl,
cyclohexyl, cycloheptyl, cyclooctyl and cyclododecyl. Preferred
groups are cyclopentyl and cyclohexyl.
[0049] In the context of the invention the aryl substituent may be
naphthyl or preferably phenyl.
[0050] In the context of the invention the heteroaryl substituent
contains preferably 5 or 6 ring atoms and preferably 1 to 3, more
preferably 1 or 2 heteroatoms selected from the group consisting of
O, S and N. Some examples are pyridinyl, pyrimidinyl, furanyl,
pyrrolyl and thiophenyl.
[0051] In the context of the invention the cycloalkyl-alkyl
substituent is preferably cycloalkyl-methyl or -ethyl, and
cycloalkyl means preferably cyclopentyl or cyclohexyl.
[0052] In the context of the invention the aralkyl substituent is
preferably arylmethyl or -ethyl, and aryl means preferably phenyl
or naphthyl. Some examples are benzyl, phenylethyl and
naphthylmethyl.
[0053] In the context of the invention the heteroaralkyl
substituent is preferably heteroarylmethyl or -ethyl, and the
heteroaryl contains preferably 5 or 6 ring atoms and preferably 1
to 3, more preferably 1 or 2 heteroatoms selected from group
consisting of O, S and N. Some examples are pyridinylmethyl or
-ethyl, pyrimidinyl, furanylmethyl, pyrrolylmethyl and
thiophenylmethyl.
[0054] In the context of the invention the alkoxy substituent may
be linear or branched and contains preferably 1 to 12 C-atoms, more
preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms and
particularly preferred 1 to 4 C-atoms. Some examples are methoxy,
ethoxy, n- or i-propoxy, n-, i- or t-butoxy, and the isomers of
pentoxy, hexoxy, heptoxy, octoxy, nonyloxy, decyloxy, undecyloxy,
dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy,
hexadecyloxy, heptadecyloxy and octadecyloxy.
[0055] In the context of the invention the cycloalkyloxy
substituent contains preferably 4 to 8 and more preferred 5 to 7
ring carbon atoms. Examples are cyclopropyloxy, cyclobutyloxy,
cyclopentyloxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy and
cyclododecyloxy. Preferred groups are cyclopentyloxy and
cyclohexyloxy.
[0056] In the context of the invention the aryloxy substituent may
be naphthyloxy or preferably phenyloxy.
[0057] In the context of the invention the heteroaryloxy
substituent contains preferably 5 or 6 ring atoms and preferably 1
to 3, more preferably 1 or 2 heteroatoms selected from group
consisting of O, S and N. Some examples are pyridinyloxy,
pyrimidinyloxy, furanyloxy, pyrrolyloxy and thiophenyloxy.
[0058] In the context of the invention the cycloalkyl-alkyloxy
substituent is preferably cycloalkylmethyloxy or -ethyloxy, and
cycloalkyl means preferably cyclopentyl or cyclohexyl.
[0059] In the context of the invention the aralkyloxy substituent
is preferably arylmethyloxy or -ethyloxy, and aryl means preferably
phenyl or naphthyl. Some examples are benzyloxy, phenylethyloxy and
naphthylmethyloxy.
[0060] In the context of the invention the heteroaralkyloxy
substituent is preferably heteroarylmethyl or -ethyl, and the
heteroaryl contains preferably 5 or 6 ring atoms and preferably 1
to 3, more preferably 1 or 2 heteroatoms selected from the group
consisting of O, S and N. Some examples are pyridinylmethyloxy or
-ethyloxy, pyrimidinyloxy, furanylmethyloxy, pyrrolylmethyloxy and
thiophenylmethyloxy.
[0061] In the context of the invention the alkylthio substituent
may be linear or branched and contains preferably 1 to 12 C-atoms,
more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms and
particularly preferred 1 to 4 C-atoms. Some examples are
methylthio, ethylthio, n- or i-propylthio, n-, i- or t-butylthio,
and the isomers of pentylthio, hexylthio, heptylthio, octylthio,
nonylthio, decylthio, undecylthio, dodecylthio, tridecylthio,
tetradecylthio, pentadecylthio, hexadecylthio, heptadecylthio and
octadecylthio.
[0062] In the context of the invention the cycloalkylthio
substituent contains preferably 4 to 8 and more preferred 5 to 7
ring carbon atoms. Examples are cyclopropylthio, cyclobutylthio,
cyclopentylthio, cyclohexylthio, cycloheptylthio, cyclooctylthio
and cyclododecylthio. Preferred groups are cyclopentylthio and
cyclohexylthio.
[0063] In the context of the invention the arylthio substituent may
be naphthylthio or preferably phenylthio.
[0064] In the context of the invention the heteroarylthio
substituent contains preferably 5 or 6 ring atoms and preferably 1
to 3, more preferably 1 or 2 heteroatoms selected from the group
consisting of O, S and N. Some examples are pyridinylthio,
pyrimidinylthio, furanylthio, pyrrolylthio and thiophenylthio.
[0065] In the context of the invention the cycloalkyl-alkylthio
substituent is preferably cycloalkylmethylthio or -ethylthio, and
cycloalkyl means preferably cyclopentyl or cyclohexyl.
[0066] In the context of the invention the aralkylthio substituent
is preferably arylmethylthio or -ethylthio, and aryl means
preferably phenyl or naphthyl. Some examples are benzylthio,
phenylethylthio and naphthylmethylthio.
[0067] In the context of the invention the heteroaralkylthio
substituent is preferably heteroarylmethylthio or -ethylthio, and
the heteroaryl contains preferably 5 or 6 ring atoms and preferably
1 to 3, more preferably 1 or 2 heteroatoms selected from group
consisting of O, S and N. Some examples are pyridinylmethylthio or
-ethylthio, pyrimidinylthio, furanylmethylthio, pyrrolylmethylthio
and thiophenylmethylthio.
[0068] In the context of the invention the alkyl-SO-- or
--SO.sub.2-- substituent may be linear or branched and contains
preferably 1 to 12 C-atoms, more preferably 1 to 8 C-atoms, most
preferably 1 to 6 C-atoms and particularly preferred 1 to 4
C-atoms. Some examples are methyl-SO-- or -- SO.sub.2--, ethyl-SO--
or --SO.sub.2--, n- or i-propyl-SO-- or --SO.sub.2--, n-, i- or
t-butyl-SO-- or --SO.sub.2--, and the isomers of pentyl-SO-- or
--SO.sub.2--, hexyl-SO-- or --SO.sub.2--, heptyl-SO-- or
--SO.sub.2--, octyl-SO-- or --SO.sub.2--, nonyl-SO-- or
--SO.sub.2--, decyl-SO-- or --SO.sub.2--, undecyl-SO-- or
--SO.sub.2--, dodecyl-SO-- or --SO.sub.2--, tridecyl-SO-- or
--SO.sub.2--, tetradecyl-SO-- or --SO.sub.2--, pentadecyl-SO-- or
--SO.sub.2--, hexadecyl-SO-- or -- SO.sub.2--, heptadecyl-SO-- or
--SO.sub.2-- and octadecyl-SO-- or --SO.sub.2--.
[0069] In the context of the invention the cycloalkyl-SO-- or
--SO.sub.2-- substituent contains preferably 4 to 8 and more
preferred 5 to 7 ring carbon atoms. Examples are cyclopropyl-SO--
or --SO.sub.2--, cyclobutyl-SO-- or --SO.sub.2--, cyclopentyl-SO--
or --SO.sub.2--, cyclohexyl-SO-- or --SO.sub.2-- cycloheptyl-SO--
or --SO.sub.2--, cyclooctyl-SO-- or --SO.sub.2-- and
cyclododecyl-SO-- or --SO.sub.2--. Preferred groups are
cyclopentyl-SO-- or --SO.sub.2-- and cyclohexyl-SO-- or
--SO.sub.2--.
[0070] In the context of the invention the aryl-SO-- or
--SO.sub.2-- substituent may be naphthyl-SO-- or --SO.sub.2-- or
preferably phenyl-SO-- or --SO.sub.2--.
[0071] In the context of the invention the heteroaryl-SO-- or
--SO.sub.2-- substituent contains preferably 5 or 6 ring atoms and
preferably 1 to 3, more preferably 1 or 2 heteroatoms selected from
the group consisting of O, S and N. Some examples are
pyridinyl-SO-- or --SO.sub.2--, pyrimidinyl-SO-- or --SO.sub.2--,
furanyl-SO-- or --SO.sub.2--, pyrrolyl-SO-- or --SO.sub.2-- and
thiophenyl-SO-- or --SO.sub.2--.
[0072] In the context of the invention the cycloalkyl-alkyl-SO-- or
--SO.sub.2-- substituent is preferably cycloalkyl-methyl-SO-- or
--SO.sub.2-- or --ethyl-SO-- or --SO.sub.2--, and cycloalkyl means
preferably cyclopentyl or cyclohexyl.
[0073] In the context of the invention the aralkyl-SO-- or
--SO.sub.2-- substituent is preferably arylmethyl-SO-- or
--SO.sub.2-- or --ethyl-SO-- or --SO.sub.2--, and aryl means
preferably phenyl-SO-- or --SO.sub.2-- or naphthyl-SO-- or
--SO.sub.2--. Some examples are benzyl-SO-- or --SO.sub.2--,
phenylethyl-SO-- or --SO.sub.2-- and naphthylmethyl-SO-- or
--SO.sub.2--.
[0074] In the context of the invention the heteroaralkyl-SO-- or
--SO.sub.2-- substituent is preferably heteroarylmethyl-SO-- or
--SO.sub.2-- or --ethyl-SO-- or --SO.sub.2--, and the heteroaryl
contains preferably 5 or 6 ring atoms and preferably 1 to 3, more
preferably 1 or 2 heteroatoms selected from the group consisting of
O, S and N. Some examples are pyridinylmethyl-SO-- or --SO.sub.2--
or --ethyl-SO-- or --SO.sub.2--, pyrimidinyl-SO-- or --SO.sub.2--,
furanylmethyl-SO-- or --SO.sub.2--, pyrrolylmethyl-SO-- or
-SO.sub.2-- and thiophenylmethyl-SO-- or --SO.sub.2--.
[0075] In the context of the invention the alkyl-CO-- substituent
may be linear or branched and contains preferably 1 to 12 C-atoms,
more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms and
particularly preferred 1 to 4 C-atoms. Some examples are
methyl-CO--, ethyl-CO--, n- or i-propyl-CO--, n-, i- or
t-butyl-CO--, and the isomers of pentyl-CO--, hexyl-CO--,
heptyl-CO--, octyl-CO--, nonyl-CO--, decyl-CO--, undecyl-CO--,
dodecyl-CO-, tridecyl-CO--, tetradecyl-CO--, pentadecyl-CO--,
hexadecyl-CO--, heptadecyl-CO-- and octadecyl-CO--.
[0076] In the context of the invention the cycloalkyl-CO--
substituent contains preferably 4 to 8 and more preferred 5 to 7
ring carbon atoms. Examples are cyclopropyl-CO--, cyclobutyl-CO--,
cyclopentyl-CO--, cyclohexyl-CO--, cycloheptyl-CO--,
cyclooctyl-CO-- and cyclododecyl-CO--. Preferred groups are
cyclopentyl-CO-- and cyclohexyl-CO--.
[0077] In the context of the invention the aryl-CO-- substituent
may be naphthyl-CO-- or preferably phenyl-CO--.
[0078] In the context of the invention the heteroaryl substituent
contains preferably 5 or 6 ring atoms and preferably 1 to 3, more
preferably 1 or 2 heteroatoms selected from group consisting of O,
S and N. Some examples are pyridinyl, pyrimidinyl, furanyl,
pyrrolyl and thiophenyl.
[0079] In the context of the invention the cycloalkyl-alkyl-CO--
substituent is preferably cycloalkyl-methyl-CO--- or --ethyl-CO--,
and cycloalkyl means preferably cyclopentyl or cyclohexyl.
[0080] In the context of the invention the aralkyl-CO-- substituent
is preferably arylmethyl-CO-- or --ethyl-CO--, and aryl means
preferably phenyl-CO-- or naphthyl-CO--. Some examples are
benzyl-CO--, phenylethyl-CO-- and naphthylmethyl-CO--.
[0081] In the context of the invention the heteroaralkyl-CO--
substituent is preferably heteroarylmethyl-CO-- or --ethyl-CO--,
and the heteroaryl contains preferably 5 or 6 ring atoms and
preferably 1 to 3, more preferably 1 or 2 heteroatoms selected from
group consisting of O, S and N. Some examples are
pyridinylmethyl-CO-- or --ethyl-CO--, pyrimidinyl-CO--,
furanylmethyl-CO--, pyrrolylmethyl-CO-- and
thiophenylmethyl-CO--.
[0082] In the context of the invention the alkoxyalkyl substituent
contains preferably in total 2 to 12, more preferably 2 to 8 and
most preferably 2 to 6 carbon atoms. The alkoxy may contain 1 to 4
carbon atoms. Some examples are methoxyethyl, methoxyethyl,
methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl,
ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxypentyl,
ethoxyhexyl, propoxymethyl and butoxymethyl.
[0083] In the context of the invention the
polyoxyalkylene-O-R.sub.6 substituent preferably contains 2 to 12
and more preferably 2 to 6 oxyalkylene units, wherein alkylene is
preferably ethylene, 1,2- or 1,3-propylene or 1,2-, 1,3- or
1,4-butylene. R.sub.6 is preferably H or C.sub.1 to
C.sub.4alkyl.
[0084] In the context of the invention R.sub.3 and R.sub.4 in the
meaning of alkyl may be linear or branched and contain preferably 1
to 12 C-atoms, more preferably 1 to 8 C-atoms, most preferably 1 to
6 C-atoms and particularly preferred 1 to 4 C-atoms. Some examples
are methyl, ethyl, n- or i-propyl, n-, i- or t-butyl, and the
isomers of pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl,
dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl
and octadecyl.
[0085] In the context of the invention R.sub.3 and R.sub.4 in the
meaning of alkylphenyl may be preferably C.sub.1 to
C.sub.8alkylphenyl, C.sub.1 to C.sub.4alkylphenyl. Some examples
are methylphenyl, ethylphenyl, n- or i-propylphenyl, n-, i- or
t-butylphenyl, hexylphenyl, octylphenyl, dodecylphenyl, and
dimethylphenyl.
[0086] In the context of the invention R.sub.3 and R.sub.4 in the
meaning of alkylbenzyl may be preferably C.sub.1 to
C.sub.8alkylbenzyl, C.sub.1 to C.sub.4alkylbenzyl. Some examples
are methylbenzyl, ethylbenzyl, n- or i-propylbenzyl, n-, i- or
t-butylbenzyl, hexylbenzyl, octylbenzyl, dodecylbenzyl, and
dimethylbenzyl.
[0087] In the context of the invention R.sub.3 and R.sub.4 mean
independently from one another preferably H, C.sub.1 to
C.sub.4alkyl, cyclohexyl, phenyl, benzyl, C.sub.1 to
C.sub.4alkylphenyl or C.sub.1 to C.sub.4alkylbenzyl, or R.sub.3 and
R.sub.4 together mean tetramethylene, pentamethylene, or the group
--CH.sub.2-CH.sub.2-O-CH.sub.2-CH.sub.2--.
[0088] In the context of the invention R.sub.5 in the meaning of
alkylene is preferably C.sub.1 to C.sub.6alkylene, C.sub.1 to
C.sub.4alkylene, for example methylene, ethylene, propylene or
butylene. Most preferred R.sub.5 is methylene, ethylene, phenylene
or benzylene.
[0089] In the context of the invention wherein R.sub.6 is alkyl, it
may be linear or branched and contain preferably 1 to 12 C-atoms,
more preferably 1 to 8 C-atoms, most preferably 1 to 6 C-atoms and
particularly preferred 1 to 4 C-atoms. Some examples are methyl,
ethyl, n- or i-propyl, n-, i- or t-butyl, and the isomers of
pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,
tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl and
octadecyl. R.sub.6 is preferably H, C.sub.1 to C.sub.12alkyl,
cyclopentyl, cyclohexyl, phenyl, benzyl.
[0090] Examples for substituents are F, Cl, Br, methyl, ethyl,
propyl, butyl, hexyl, methyloxy, ethyloxy, propyloxy, butyloxy,
hexyloxy, methylthio, ethylthio, methyl- or ethyl-SO--, methyl- or
ethyl-SO.sub.2--, phenyl, benzyl, toluyl, xylyl, methylbenzyl,
dimethylbenzyl, chlorophenyl, dichlorophenyl, methoxyphenyl,
dimethoxyphenyl, methoxybenzyl, dimethoxybenzyl, CH.sub.3-CO--,
C.sub.6H.sub.5-CO--, CH.sub.3-CO-O--, C.sub.6H.sub.5-CO-O--,
CH.sub.3-SO.sub.2-O--, C.sub.6H.sub.5-SO.sub.2-O--, --NH.sub.2,
--NHCH.sub.3, --NHC.sub.2H.sub.5, --NHC.sub.8H.sub.17,
--N(CH.sub.3).sub.2, --COOH, --CO-OCH.sub.3, --CO-OC.sub.2H.sub.5,
SO.sub.3H, --SO.sub.2-OCH.sub.3, SO.sub.2-OC.sub.2H.sub.5,
--CO-NH.sub.2, --CO-NCH.sub.3, --CO-NHC.sub.2H.sub.5,
--CO-NHC.sub.8H.sub.17, --CO-NH(CH.sub.3).sub.2,
--SO.sub.2-NH.sub.2, --SO.sub.2-NHCH.sub.3, --
SO.sub.2-NHC.sub.2H.sub.5, --SO.sub.2-NHC.sub.8H.sub.17,
--SO.sub.2-N(CH.sub.3).sub.2, H.sub.2N-SO.sub.2--, methoxymethyl,
methoxyethyl, ethoxyethyl, --(OCH.sub.2CH.sub.2).sub.2-OH, --CN and
--NO.sub.2.
[0091] The number of substituents is arbitrary and depends
essentially upon synthetic possibilities, the desired optical
properties related to fluorescence and absorption, and the desired
solubility.
[0092] In a preferred embodiment of the invention the compounds of
formula I correspond to formula II, 2
[0093] wherein
[0094] R.sub.7, R.sub.8, R.sub.9 and R.sub.10 independently from
one another can be H, F, Cl, Br, I, C.sub.1 to C.sub.18alkyl,
C.sub.1 to C.sub.18alkoxy, C.sub.1 to C.sub.18alkylthio, aryl,
aralkyl, C.sub.1 to C.sub.12alkyl-aryl or C.sub.1 to
C.sub.12alkyl-aralkyl, and the ring 2 is unsubstituted or
substituted as described before, including the preferred
substituents.
[0095] Preferably at least one of R.sub.7, R.sub.8, R.sub.9 and
R.sub.10 is one of the defined substituents. More preferably
R.sub.8 and R.sub.9 are one of the defined substituents. Mostly
preferred R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are
substituents.
[0096] In the context of the invention when R.sub.7, R.sub.8,
R.sub.9 and R.sub.10 mean linear alkyl or branched alkyl they
contain preferably 1 to 12 C-atoms, more preferably 1 to 8 C-atoms,
most preferably 1 to 6 C-atoms and particularly preferred 1 to 4
C-atoms. Some examples are methyl, ethyl, n-or i-propyl, n-, i- or
t-butyl, and the isomers of pentyl, hexyl, heptyl, octyl, nonyl,
decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,
hexadecyl, heptadecyl and octadecyl.
[0097] In the context of the invention when R.sub.7, R.sub.8,
R.sub.9 and R.sub.10 mean linear alkoxy or alkoxy branched they
contain preferably 1 to 12 C-atoms, more preferably 1 to 8 C-atoms,
most preferably 1 to 6 C-atoms and particularly preferred 1 to 4
C-atoms. Some examples are methoxy, ethoxy, n- or i-propoxy, n-, i-
or t-butoxy, and the isomers of pentoxy, hexoxy, heptoxy, octoxy,
nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy,
tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy and
octadecyloxy.
[0098] In the context of the invention when R.sub.7, R.sub.8,
R.sub.9 and R.sub.10 mean linear alkylthio or alkylthio branched
they contain preferably 1 to 12 C-atoms, more preferably 1 to 8
C-atoms, most preferably 1 to 6 C-atoms and particularly preferred
1 to 4 C-atoms. Some examples are methylthio, ethylthio, n- or
i-propylthio, n-, i- or t-butylthio, and the isomers of pentylthio,
hexylthio, heptylthio, octylthio, nonylthio, decylthio,
undecylthio, dodecylthio, tridecylthio, tetradecylthio,
pentadecylthio, hexadecylthio, heptadecylthio and
octadecylthio.
[0099] In the context of the invention R.sub.7, R.sub.8, R.sub.9
and R.sub.10 may be aryl naphthyl or preferably phenyl.
[0100] In the context of the invention R.sub.7, R.sub.8, R.sub.9
and R.sub.10 may be aralkyl preferably arylmethyl or -ethyl,
wherein aryl means preferably phenyl or naphthyl. Some examples are
benzyl, phenylethyl and naphthylmethyl.
[0101] In the context of the invention when R.sub.7, R.sub.8,
R.sub.9 and R.sub.10 are alkyl-aryl they are preferably
alkylphenyl, more preferably C.sub.1 to C.sub.8alkylphenyl, and
most preferably C.sub.1 to C.sub.4alkylphenyl. Some examples are
methylphenyl, ethylphenyl, n- or i-propylphenyl, n-, i- or
t-butylphenyl, hexylphenyl, octylphenyl, dodecylphenyl, and
dimethylphenyl.
[0102] In the context of the invention when R.sub.7, R.sub.8,
R.sub.9 and R.sub.10 are alkyl-aralkyl they are preferably
alkyl-benzyl, more preferably C.sub.1 to C.sub.8alkylbenzyl, and
most preferably C.sub.1 to C.sub.4alkylbenzyl.
[0103] Some examples are methylbenzyl, ethylbenzyl, n- or
i-propylbenzyl, n-, i- or t-butylbenzyl, hexylbenzyl, octylbenzyl,
dodecylbenzyl, and dimethylbenzyl.
[0104] In an especially preferred embodiment of the invention the
ring 2 is also substituted, particularly in the 7-position, in the
8-position or in both with in organic group substituent.
[0105] In a particularly preferred embodiment of the invention the
compounds of formula II corresponds to formula III, 3
[0106] wherein
[0107] R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are Cl, phenyl or
C.sub.1 to C.sub.12alkylphenyl,
[0108] R.sub.11 is H or an organic group substituent, and
[0109] R.sub.12 is H or an organic group substituent.
[0110] The ring 2 is preferably monosubstituted, meaning that one
of R.sub.1 and R.sub.12 is an organic group substituent.
[0111] Particularly preferred R.sub.7, R.sub.8, R.sub.9 and
R.sub.10 are chlorine or phenyl.
[0112] In the context of the invention when R.sub.11 or R.sub.12
organic group substituents they are preferably selected from the
group consisting of --CN, --NO.sub.2, --COOH, C.sub.1 to
C.sub.18alkyl, C.sub.2 to C.sub.18alkenyl, C.sub.2 to
C.sub.18alkinyl, C.sub.1 to C.sub.18hydroxyalkyl, C.sub.1 to
C.sub.18halogenalkyl, C.sub.3 to C.sub.12cycloalkyl, C.sub.6 to
C.sub.18 aryl, C.sub.3 to C.sub.12 cycloalkyl-alkyl, C.sub.1 to
C.sub.18 aralkyl, C.sub.6 to C.sub.18 alkyloxy, C.sub.3 to C.sub.12
cycloalkyloxy, C.sub.6 to C.sub.18 aryloxy, C.sub.3 to C.sub.12
cycloalkyl-alkyloxy, C.sub.6 to C.sub.18 aralkyloxy, C.sub.1 to
C.sub.18 alkylthio, C.sub.3 to C.sub.12 cycloalkylthio, C.sub.6 to
C.sub.18 arylthio, C.sub.3 to C.sub.12 cycloalkyl-alkylthio,
C.sub.6 to C.sub.18 aralkylthio, C.sub.1 to C.sub.18 alkyl-CO--,
C.sub.3 to C.sub.12 cycloalkyl-CO--, C.sub.6 to C.sub.18aryl-CO--,
C.sub.3 to C.sub.12 cycloalkylalkyl-CO--, C.sub.6 to C.sub.18
aralkyl-CO--, --NR.sub.3R.sub.4, alkoxyalkyl with 2 to 20 carbon
atoms, polyoxyalkylene-OR.sub.6,
--X-(R.sub.5).sub.k-C(O)-NR.sub.3R.sub.4,
--X-(R.sub.5).sub.k-C(O)-OR.sub.6,
--X-(R.sub.5).sub.k-SO.sub.2-OR.sub.6,
--X-(R.sub.5).sub.k-SO.sub.2-NR.sub.3R.sub.4, --NH-C(O)-R.sub.6 and
--O-C(O)-R.sub.6,
[0113] wherein
[0114] R.sub.3 and R.sub.4 independently from one another can be H,
C.sub.1 to C.sub.20alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl,
C.sub.1 to C.sub.12alkylphenyl or C.sub.1 to C.sub.12alkylbenzyl,
or R.sub.3 and R.sub.4 together mean tetramethylene,
pentamethylene, or the groups
--CH.sub.2-CH.sub.2-O-CH.sub.2-CH.sub.2-- or
--CH.sub.2-CH.sub.2-NR.sub.3-CH.sub.2-CH.sub.2--,
[0115] R.sub.5 is C.sub.1 to C.sub.12alkylene, phenylene or
benzylene,
[0116] R.sub.6 means H, C.sub.1 to C.sub.20alkyl, cyclopentyl,
cyclohexyl, phenyl, benzyl, C.sub.1 to C.sub.12alkylphenyl or
[0117] C.sub.1 to C.sub.12alkylbenzyl,
[0118] X is a direct bond, --O-- or S,
[0119] k is 0 or 1 and
[0120] and the salts of the acids.
[0121] The preferred meanings described before are also valid for
the meanings of R.sub.11, R.sub.12, X and R.sub.3 to R.sub.6.
[0122] when R.sub.11 and R.sub.12 are organic group substituents
they are most preferably selected from the group consisting of
--CN, --NO.sub.2, C.sub.1 to C.sub.18 alkyl, C.sub.1 to C.sub.18
hydroxyalkyl, C.sub.5 to C.sub.7 cycloalkyl, C.sub.6 to
C.sub.10aryl, C.sub.7 to C.sub.11 aralkyl, C.sub.1 to
C.sub.18alkyloxy, C.sub.3 to C.sub.12cycloalkyloxy, C.sub.6 to
C.sub.10aryloxy, C.sub.5 to C.sub.7 cycloalkyl-alkyloxy, C.sub.7 to
C.sub.11 aralkyloxy, C.sub.1 to C.sub.18 alkylthio, C.sub.5 to
C.sub.7 cycloalkylthio, C.sub.6 to C.sub.10 arylthio, C.sub.5 to
C.sub.7 cycloalkyl-alkylthio, C.sub.7 to C.sub.11 aralkylthio,
C.sub.1 to C.sub.18 alkyl-CO--, C.sub.5 to C.sub.7 cycloalkyl-CO--,
C.sub.6 to C.sub.10aryl-CO--, C.sub.5 to C.sub.7
cycloalkyl-alkyl-CO--, C.sub.7 to C.sub.11 aralkyl-CO--,
--NR.sub.3R.sub.4, alkoxyalkyl with 2 to 12 carbon atoms,
polyoxyalkylene-OR.sub.6, --X-(R.sub.5).sub.k-C(O)-NR.sub.3R.sub.4-
, --X-(R.sub.5).sub.k-C(O)-OR.sub.6,
--X-(R.sub.5).sub.k-SO.sub.2-OR.sub.6- ,
--X-(R.sub.5).sub.k-SO.sub.2-NR.sub.3R.sub.4, --NH-C(O)-R.sub.6 and
--O-C(O)-R.sub.6,
[0123] wherein
[0124] R.sub.3 and R.sub.4 independently from one another mean H,
C.sub.1 to C.sub.6alkyl, cyclopentyl, cyclohexyl, phenyl, benzyl,
C.sub.1 to C.sub.6alkylphenyl or C.sub.1 to C.sub.6alkylbenzyl, or
R.sub.3 and R.sub.4 together mean tetramethylene, pentamethylene,
or the group --CH.sub.2-CH.sub.2-O-CH.sub.2-CH.sub.2--,
[0125] R.sub.5 is C.sub.1 to C.sub.4alkylene, phenylene or
benzylene,
[0126] R.sub.6 means H, Cl to C.sub.12alkyl, cyclopentyl,
cyclohexyl, phenyl, benzyl, C.sub.1 to C.sub.6alkylphenyl or
C.sub.1 to C.sub.6alkylbenzyl,
[0127] X is a direct bond, --O-- or S,
[0128] k is 0 or 1 and
[0129] and the salts of the acids.
[0130] In an especially preferred embodiment of the invention
R.sub.11 and R.sub.12 are selected from the group consisting of
--NO.sub.2, C.sub.1 to C.sub.18 alkyl, which is linear or branched,
C.sub.1 to C.sub.18 alkyloxy, which is linear or branched,
--C(O)OH, or --C(O)-O-C.sub.1 to C.sub.18alkyl.
[0131] The compounds of formula I to III are partially known or can
be easily prepared from unsubstituted or substituted
orthophenylenediamines and from unsubstituted or substituted
phthalic anhydride as for example described in EP-A-0 456 609.
[0132] The guest chromophore can be selected from a broad range of
pigments, pigment derivatives, dyes and their derivatives and
mixtures thereof, so long as they are luminescent in the molecular
state, and their absorption spectra do overlap with the emission
spectrum of the host chromophore. Some guest chromophores are for
example described in WO 93/23492.
[0133] In one embodiment of this invention, the guest chromophore
preferably is soluble, at least to some extent, in a solvent,
and--if desired--in the host chromophore, allowing formation of
homogeneous solid solutions.
[0134] Solubility of a guest chromophore means in the context of
the invention that at least 200 mg, more preferably at least 300 mg
and most preferably at least 500 mg of the guest chromophore are
soluble in 1 liter of solvent like dimethylformamide at 20.degree.
C. This definition employs also to compositions where the host and
guest chromophores are embedded in a polymer matrix.
[0135] The guest chromophore may be selected from the group
consisting of quinacridones, perylenes, perinones, diketo- and
dithioketopyrrolopyrrole- s, rhodamines, coumarins, xanthens,
oxazines, oxazoles, cyanines, phthalocyanines, porphyrines, styryl
dyes, metal complexes and mixtures thereof.
[0136] Preferred guest chromophores are selected from group
consisting of quinacridones, perylenes, perinones,
diketopyrrolopyrroles, rhodamines, coumarins, cyanines,
phthalocyanines, porphyrines, styryl dyes and mixtures thereof.
Especially preferred are quinacridones, perylenes,
diketopyrrolopyrroles, rhodamines, coumarins and mixtures
thereof.
[0137] The guest compounds and their derivatives are well known in
the art or can be prepared by analogous processes.
[0138] Quinacridones can be found described in Chemical Reviews 67
(1) pages 1 to 18 (1967).
[0139] The quinacridones may correspond to the formula VII 4
[0140] wherein
[0141] R.sub.26 to R.sub.29 and R.sub.32 to R.sub.35 independently
from one another can be H, C.sub.1 to C.sub.6alkyl, C.sub.1 to
C.sub.6alkoxy, F, Cl, Br, CN, NO.sub.2, or --NR.sub.21R.sub.22,
wherein R.sub.2, and R.sub.22 independently from one another are H,
C.sub.1 to C.sub.20alkyl, phenyl, C.sub.1 to C.sub.12alkylphenyl,
benzyl or C.sub.1 to C.sub.12alkylbenzyl, or R.sub.21 and R.sub.22
together mean tetramethylene, pentamethylene or
--CH.sub.2CH.sub.2-O-CH.sub.2CH.sub.2--- ; or two neighbored
residues of R.sub.26 to R.sub.29 and/or R.sub.32 to R.sub.35
together with carbon atoms, to which they are linked, a 5- or
6-membered aliphatic, heteroaliphatic, aromatic or heteroaromatic
ring, whereby the heteroatoms are selected from the group of --O--,
--S-- and N; and
[0142] R.sub.30 and R.sub.31 independently from one another are H,
C.sub.1 to C.sub.18alkyl, C.sub.2 to C.sub.18alkenyl, C.sub.2 to
C.sub.18alkinyl, phenyl, benzyl, C.sub.1 to C.sub.6alkylphenyl,
C.sub.1 to C.sub.6alkylbenzyl or R.sub.36-O-C(O)--, wherein
R.sub.36 means C.sub.1 to C.sub.18alkyl, C.sub.2 to
C.sub.18alkenyl, C.sub.2 to C.sub.18alkinyl, phenyl, benzyl,
C.sub.1 to C.sub.6alkylphenyl, or C.sub.1 to
C.sub.6alkylbenzyl.
[0143] Perylenes can be found described in U.S. Pat. Nos. 4,446,324
and 5,470,502. Preferred examples are those perylenes of formulae
IX and X, 5
[0144] wherein
[0145] R.sub.37 and R.sub.38 independently from one another can be
F, Cl, Br, or CN,
[0146] R.sub.39 and R.sub.40 independently from one another mean
R.sub.36-O-C(O)--, wherein R.sub.36 means C.sub.1 to C.sub.18alkyl,
C.sub.2 to C.sub.18alkenyl, C.sub.2 to C.sub.18alkinyl, phenyl,
benzyl, C.sub.1 to C.sub.6alkyl phenyl, or C.sub.1 to
C.sub.6alkylbenzyl.
[0147] R.sub.41 and R.sub.42 independently from one another can be
H, C.sub.1 to C.sub.18alkyl, C.sub.2 to C.sub.18alkenyl, C.sub.2 to
C.sub.18alkinyl, phenyl, benzyl, C.sub.1 to C.sub.6alkylphenyl,
C.sub.1 to C.sub.6alkylbenzyl or R.sub.36-O-C(O)--, wherein
R.sub.36 means C.sub.1 to C.sub.18alkyl, C.sub.2 to
C.sub.18alkenyl, C.sub.2 to C.sub.18alkinyl, phenyl, benzyl,
C.sub.1 to C.sub.6alkylphenyl, or C.sub.1 to C.sub.6alkyl benzyl,
and
[0148] the R.sub.43 independently from one another are C.sub.1 to
C.sub.18alkoxy, phenoxy or C.sub.1 to C.sub.12alkylphenoxy.
[0149] Some examples are the commercially available compounds are
shown; 6
[0150] Diketo- amd dithioketopyrrolopyrroles can be found described
in U.S. Pat. No. 4,415,685 and JP-A-61 162 555.
[0151] Examples for diketopyrrolopyrroles correspond to the formula
XI, 7
[0152] wherein
[0153] the R.sub.44 independently from one another are H, halogen,
or phenyl which is unsubstituted or substituted with C.sub.1 to
C.sub.6alkyl, C.sub.1 to C.sub.6alkoxy, phenyl, C.sub.1 to
C.sub.4alkylphenyl, F, Cl, Br, CN, NO.sub.2, or
--NR.sub.21R.sub.22, wherein R.sub.21 and R.sub.22 independently
from one another are H, C.sub.1 to C.sub.20alkyl, phenyl, C.sub.1
to C.sub.12alkylphenyl, benzyl or C.sub.1 to C.sub.12alkylbenzyl,
or R.sub.21 and R.sub.22 together mean tetramethylene,
pentamethylene or --CH.sub.2CH.sub.2-O-CH.sub.2CH.sub.2--- ;
and
[0154] the R.sub.45 independently from one another mean H, C.sub.1
to C.sub.18alkyl, C.sub.2 to C.sub.18alkenyl, C.sub.2 to
C.sub.18alkinyl, phenyl, benzyl, C.sub.1 to C.sub.6alkyl phenyl, or
C.sub.1 to C.sub.6alkylbenzyl, or R.sub.30-O-C(O)--, wherein
R.sub.30 means C.sub.1 to C.sub.18alkyl, C.sub.2 to
C.sub.18alkenyl, C.sub.2 to C.sub.18alkinyl, phenyl, benzyl,
C.sub.1 to C.sub.6alkylphenyl, or C.sub.1 to C.sub.6alkyl
benzyl.
[0155] A range of commercial rhodamines are available from ACROS
ORGANICS catalogue of fine chemicals Vol. 1 (1996).
[0156] Preferred examples of rhodamines are those of the formula
XII, 8
[0157] wherein
[0158] wherein R.sub.21 and R.sub.22 independently from one another
are H, C.sub.1 to C.sub.20alkyl, phenyl, C.sub.1 to
C.sub.12alkylphenyl, benzyl or C.sub.1 to C.sub.12alkylbenzyl, or
R.sub.21 and R.sub.22 together mean tetramethylene, pentamethylene
or --CH.sub.2CH.sub.2-O-CH.sub.2CH.sub.2--- ;
[0159] R.sub.46 means H, C.sub.1 to C.sub.18alkyl, C.sub.2 to
C.sub.18alkenyl, C.sub.2 to C.sub.18alkinyl, phenyl, benzyl,
C.sub.1 to C.sub.6alkyl phenyl, or C.sub.1 to C.sub.6alkylbenzyl,
or an equivalent of a metal or ammonium cation;
[0160] and R.sub.47 means the group .dbd.NR.sub.48, or the group
.dbd..sup.+NR.sub.48R.sub.49X.sup.-, R.sub.48 and R.sub.49
independently from one another are H, C.sub.1 to C.sub.18alkyl,
phenyl, C.sub.1 to C.sub.12alkylphenyl, benzyl or C.sub.1 to
C.sub.12alkylbenzyl; and X is monovalent anion.
[0161] A range of commercial coumarins, oxazines, cyanines,
xanthens and styryl dyes are available from ACROS ORGANICS
catalogue of fine chemicals Vol. 1 (1996).
[0162] A range of commercial oxazoles are available from DOJINDO
LABORATORIES catalogue 18th edition (1992).
[0163] Porphyrines and phthalocyanines are for example described in
a book "The Phthalocyanines" (Frank H. Moser et. al., published by
Franklin, 1983).
[0164] In the context of the invention, effective amount of a guest
chromophore means for example, that the composition may contain
from 0.001 to 30, preferably from 0.01 to 20, more preferably from
0.01 to 10 and most preferably from 0.01 to 5 percent by weight, of
guest chromophore, related to the total amount of host and guest
chromophore.
[0165] Further, in the context of this invention, the meaning of
the overlap of the absorption spectrum of the guest chromophore
with the fluorescence emission spectrum of the host chromophore, is
clear to a skilled person in this field. However, to facilitate the
understanding to others, overlap means "spectral overlap" defined
by the following integral
S=.intg..sub.0.sup.+.infin.f.sub.F(.nu.)f.sub.A(.nu.)d.nu.
[0166] wherein f.sub.F(.nu.) is normalized, so that
.intg..sub.0.sup.+.infin.f.sub.F(.nu.) d.nu. is equal to
fluorescence quantum yield of the host, and where .nu. is the wave
number, f.sub.F the fluorescence spectrum of the host measured in
quanta, and f.sub.A the spectral distribution of the molar
extinction coefficient of the guest. The spectral overlap to
realize photoluminescence enhancement usually is greater than 10,
preferably greater than 100, more preferably greater than 500. An
upper limit makes no sense, because the quantity "overlap" has no
maximum (i.e. the larger, the better)).
[0167] In the context of this invention, embedded means a
distribution of the guest chromophore (or both host and guest
chromophore, if a polymer matrix is used) within the matrix or
total amount of host chromophore (or--accordingly, of course, the
polymer matrix). Preferably, this distribution is homogeneously.
Hence, in another preferred embodiment of this invention, (a) the
guest chromophore is homogeneously distributed within the matrix of
the host chromophore, or (b) the host chromophore and the guest
chromophore both are homogeneously distributed within the polymer
matrix.
[0168] In the context of this invention, the term "homogeneously"
means that the components within the matrix, e.g. the guest
chromophore, is evenly or uniformly distributed or dispersed
throughout the matrix (or host or host/polymer matrix), and,
preferably in the ideal case are essentially equidistant from each
other. According to observations today, the more even or uniform
the distribution is, the better are the fluorescence properties,
because the coexistence of areas having bright and weak
fluorescence are reduced as well as areas wherein the emission
color is closer to that of the host than the guest. Furthermore, a
homogeneous or even distribution is preferred, because usually the
chances for aggregation are decreased.
[0169] In another preferred embodiment of this invention, the
average particle size of the guest chromophores (or the host and
guest chromophores, if a polymer matrix is applied) are not bigger
than a desired diameter, preferably more than a desired amount of
the guest chromophores (or host and guest chromophores, if a
polymer matrix is applied) are in their molecular state. Most
preferably, the guest chromophores (or host and guest chromophores,
if a polymer matrix is applied) are molecularly dissolved and
homogeneously distributed within the matrix of the host chromophore
(or the polymer matrix).
[0170] In the context of this invention, the term "dissolved" means
that a molecule exists as a free and isolated entity in a given
matrix, preferably in such a way, that it is disengaged from any
interactions between molecules of the same species, i.e. it is
entirely surrounded by matrix molecules. Usually the matrix can be
a liquid organic solvent or a solid material such as a polymer or
another fluorescent material (host), which possesses a different
chemical structure. The concentration limits for molecules in the
dissolved state in general depend strongly on the associative
nature between the molecule and the matrix medium, and/or the
intrinsic cohesive forces that exist between the guest molecules in
question. Correspondingly, it is impossible to define universal
ranges for preferred concentrations, and therefore, usually must be
treated on an ad hoc basis, e.g. by a few simple experiments.
[0171] Polymers which may be used as polymer matrix may be selected
from thermoplastics, polymer blends, thermosettings and
structurally crosslinked polymers. The polymers may be
homopolymers, copolymers, blockpolymers, graft polymers or random
polymers.
[0172] The polymers may be opaque or translucent but preferably
transparent. The polymers may be selected for example from the
group of thermoplastic polymers like polyesters, poly amides,
polyimides, polyamide-imides, polyamide esters, polyurethanes,
polyureas, polyolefines; polymers from substituted olefines like
vinylethers, vinylesters, vinylalcohols, vinylchloride,
vinyidichloride, acetonitrile, acrylic acid, methacrylic acid,
esters and amides of acrylic acid and methacrylic acid, styrene,
chlorostyrene, methylstyrene, styrene sulfonic acid and their
esters and amides, vinylcarbazole, vinylpyridine, vinylpyrrolidone:
polymaleic acid and esters and amides therefrom; polyethers (for
example from bisphenol-A diglycidyl ether), polysulfones,
polyketones, polyphenylsulfides, and polyacetales; and natural
polymers and their derivatives like cellulose and its esters and
ethers, and starch or derivatives of starch.
[0173] Examples of thermosetting resins and structurally
crosslinked resins are polyepoxides, unsaturated polyesters,
photocrosslinked resins for example from acrylic acid and/or
methacrylic esters and/or amides from polyols and/or polyamines,
melamine/formaldehyde resins, and phenol/formaldehyde resins;
polymers from butadiene, isoprene and or chloroprene and copolymers
with olefins, which may be crosslinked and of rubbery nature,
including latices; as well as silicates obtainable through the
known sol/gel process.
[0174] The polymeric compositions of the invention may contain
further ingredients to enhance certain features such as electrical,
physical and mechanical properties, and/or the processability, for
example dispersing agents to achieve a uniform distribution of
particles, lubricants, plasticizers, antistatica, solvents, molding
agents, antioxidants, light stabilizers, fillers and reinforcing
fillers like glass balls and glass fibers, silicates (e.g. mica,
clay, wollastonite), metal and semiconductor metal oxides, metal
carbonates, metal salts, metals and semiconductor metals, carbon
black, as powder, or carbon fibers, whiskers, metal and
semiconductor metal carbides, metal and semiconductor metal
nitrides, dyes, pigments and others.
[0175] The weight ratio of (host chromophores plus guest
chromophores):polymer matrix is dependent on the actual practical
application, hence there are no well defined preferred ratios,
other than the broad range 99:1 to 1:999. In certain applications
where both color strength and fluorescence are required, then the
preferred ratios of the chromophores to the polymer matrix are
20:80 to 99:1, preferably 50:50 to 99:1 and more preferably 80:20
to 99:1. In circumstances where fluorescence is desired but color
strength is not required, then the preferred ratio of the
chromophores to the polymer matrix are 20:80 to 1:999, more
preferably 10:90 to 1:999 and more preferably 5:95 to 1:999.
[0176] The composition according to the invention can be prepared
using known processes like cosublimation, as described in JP-A-03
255 190, or new processes that utilize the solubility of the guest
chromophores.
[0177] A further embodiment of the invention is a process for the
preparation of the inventive, abovementioned composition,
comprising a host chromophore and a guest chromophore and, if
desired, a polymer matrix, wherein the absorption spectrum of the
guest chromophore overlaps with the fluorescence emission spectrum
of the host chromophore, characterized in
[0178] (a) selecting the host chromophore from the group consisting
of benzo[4,5]imidazo[2,1-a] -isoindol-11-ones,
[0179] (b) mixing the host chromophore and an effective amount of
at least one guest chromophore, and optionally a polymer or
polymerisable precursor, in the presence of a solvent, and
[0180] c) then precipitating the host and guest chromophores,
optionally in the presence the polymer of step (b), or (d)
precipitating the host and guest chromophores during polymerization
of the polymer precursor of step (b).
[0181] In the context of the invention mixing of the materials can
be achieved through dissolution of the components in a common
solvent and followed by the subsequent evaporation of the solvent;
precipitation from a good solvent into a poor solvent (vigorous
stirring can be applied); freeze-drying; and precipitation during
polymerization of polymerizable monomers or oligomers, preferably
under vigorous stirring.
[0182] Suitable inert solvents are for example protic-polar and
aprotic solvents, which may be used alone or in an admixture of at
least two solvents. Examples are: water, alcohols (methanol,
ethanol, propanol, butanol), ethyleneglycolmonomethyl- or
-monoethylether, ethers (dibutylether, tetrahydrofuran, dioxane,
ethyleneglycol dimethylether, ethyleneglycoldiethylether,
diethyleneglycoldiethylether, triethyleneglycoldimethylether),
halogenated hydrocarbons (methylenchloride, chloroform,
1,2-dichloroethane, 1,1,1-trichlororethane,
1,1,2,2-tetrachloroethane), carboxylic esters and lactones (acetic
acid ethylester, propionic acid methylester, benzoic acid
ethylester, 2-methoxyethylacetate, .gamma.-butyrolactone,
.delta.-valerolactone, pivalolac tone), carboxylic acid amides and
lactames; N,N-dimethylformamide, N,N-diethylformamide,
N,N-dimethylacetamide, tetramethylurea, hexamethylphosphorous
acidtriamide, .gamma. -butyrolactame, .epsilon.-caprolactame,
N-methylpyrrolidone, N-acetylpyrrolidone, N-methylcaprolactame;
sulfoxides (dimethylsulfoxide), sulfones (dimethylsulfone,
diethylsulfone, trimethylenesulfone, tetramethylenesulfone),
tertiary amines (N-methylpiperidine, N-methylmorpholine), aliphatic
and aromatic hydrocarbons like petroleumether, pentane, hexane,
cyclohexane, methylcyclohexane, benzene or substituted benzenes
(chlorobenzol, o-dichlorobenzene, 1,2,4-trichlorobenzene,
nitrobenzene, toluene, xylene) and nitrites (acetonitrile,
propionitrile, benzenenitrile, phenylacetonitrile), ketones
(acetone, methyl-isobutyl-ketone).
[0183] The coprecipitation may be carried out in by a number of
methods. When the host and guest chromophores possess solubilities
affording the desired weight range in the final composition, the
precipitation may be completed by adding the solution to a
non-solvent, filtering off then the precipitate and removing the
solvent, preferably in drying the solid at elevated temperatures
and preferably under vacuum. Another possibility is to simply
evaporate the solvent under vacuum and/or elevated
temperatures.
[0184] In the process of freeze-drying, a steady state of
components and solvent in general is generated by freezing a
solution, wherein the components are in homogeneous distribution.
This state is maintained upon removal of the solvent by
freeze-drying. The furnished materials are usually highly
fluorescent and exhibit all the features characteristic of
host/guest materials.
[0185] In another preferred embodiment the host and guest
chromophores are dissolved in a suitable solvent, and then this
solution is added to a polymer gel (polymer swollen with a
solvent). Usually the host and guest chromophores are in turn
soaked into the gel. As a rule, removal of the solvent and drying
generates a composition according to the invention.
[0186] In another preferred embodiment host and guest chromophores
are milled together using a ball mill. Due to the high shearing
forces usually the guest chromophore particles and/or molecules
penetrate into the host chromophore matrix, forming a fluorescent
composition according to the invention.
[0187] In another preferred embodiment the host and guest
chromophores are mixed, optionally together with a polymer, and
then melt-mixed at temperatures below the respective decomposition
temperatures of the individual components.
[0188] The compositions on hand can span a broad number of
applications. For example, the inventive compositions could be
rendered very useful as coloring agents in applications such as
road markings and traffic signs for night and daylight uses, as
they exhibit brilliant daylight fluorescence and can also be
excited by the UV radiation of motor vehicles halogen lamps,
thereby providing intense, bright colors during both day and
nighttime. Other applications include their use as pigments,
coloring agents, materials for scintillators, materials for solar
energy collectors, materials for light emitting electroluminescent
devices, materials for generating fluorescent images. Moreover, the
choice of guest compound can lend a lot of flexibility to the
desired emission wavelength required of the overall system, therein
imparting the capability for color-tuning and ease of tailoring of
the core system to specific color applications via wavelength
modulation. It is also possible to produce fluorescent images (high
relief structures) by the well known photoresist technology. The
compositions of the invention may also be used in paints, lacquers
and printing inks.
[0189] The compositions according to the invention may be used in
various forms depending upon the end use purpose.
[0190] The compositions according to the invention may be milled to
generate a powdery form for industrial applications.
[0191] Another embodiment of the invention is a composition
according to the invention in form of a powder, which contains
particles. The particles may have an average diameter from 10 nm to
500 .mu.m, more preferably 50 nm to 100 .mu.m and most preferably
50 nm to 50 .mu.m. The powders also include polymer particles
containing the host and guest chromophores dissolved and uniformly
distributed therein, and can be obtained via grinding or emulsion
polymerization, or both.
[0192] The particles of the composition of the invention may be
encapsulated with polymers by known methods to generate for example
pigments for coloring polymers. The compositions according to the
invention may be used as a coating to form a layer on support
materials, preferably via a process of co-sublimation. A further
embodiment of the invention is a support material to which on at
least partially is coated a layer of the composition according to
the invention.
[0193] Suitable support (or carrier) materials may be selected from
the group consisting of organic or inorganic materials like glass,
ceramics, minerals, plastics, paper, wood, semiconductors, metals,
metal oxides and semiconductor metal oxides, and metal or
semiconductor metalnitrides or -carbides.
[0194] The thickness of the layer depends on the desired use and
usually may be from 0.01 to 1000 .mu.m, preferably 0.05 to 500
.mu.m, and especially preferred 0.1 to 100 .mu.m.
[0195] The coatings may be protected by covering coatings which
preferably are transparent. Such coatings are well known, in
particular photocrosslinked coatings are useful for this purpose,
and are well known in the art.
[0196] The powders according to the invention may be admixed with
polymers. A further embodiment of the invention is a composition
comprising (a) a polymer substrate, and (b) particles of the
composition according to the invention, homogeneously distributed
therein.
[0197] The amount of the particles may be for example 0.0001 to 90
weight %, preferably 0.1 to 90 weight % and more preferably 1 to 50
weight % of the total composition.
[0198] The polymer substrate may be selected from thermoplastics,
polymer blends, thermosettings and structurally crosslinked
polymers. The polymers may be homopolymers, copolymers,
blockpolymers, graft polymers or random polymers.
[0199] The polymers may be opaque or translucent but preferably
transparent. The polymers may be selected for example from the
group of thermoplastic polymers like polyesters, polyamides,
polyimides, polyamide-imides, polyamide esters, polyurethanes,
polyureas, polyolefines; polymers from substituted olefines like
vinylethers, vinylesters, vinylalcohols, vinylchioride,
vinyidichloride, acetonitrile, acrylic acid, methacrylic acid,
esters and amides of acrylic acid and methacrylic acid, styrene,
chlorostyrene, methylstyrene, styrene sulfonic acid and their
esters and amides, vinylcarbazole, vinylpyridine, vinylpyrrolidone:
polymaleic acid and esters and amides therefrom; polyethers (for
example from bisphenol-A diglycidyl ether), polysufones,
polyketones, polyphenylsulfides, and polyacetales; and natural
polymers and their derivatives like cellulose and its esters and
ethers, and starch or derivatives of starch.
[0200] Examples of thermosetting resins and structurally
crosslinked resins are polyepoxides, unsaturated polyesters,
photocrosslinked resins for example from acrylic acid and/or
methacrylic esters and/or amides from polyols and/or polyamines,
melamine/formaldehyde resins, and phenol/formaldehyde resins;
polymers from butadiene, isoprene and or chloroprene and copolymers
with olefins, which may be crosslinked and of rubbery nature; as
well as silicates obtainable for example through the known sol/gel
process.
[0201] The thermoplastic compositions are for example obtainable by
known mixing methods like admixing solutions of polymers and
removing the solvent, injection molding and extrusion molding.
Thermosetting and structurally crosslinked compositions are
obtainable by known methods like press molding, whereby the
particles usually are dispersed prior to the polymerization of a
precursor composition.
[0202] The polymeric compositions of the invention may contain
further ingredients to enhance certain features such as electrical,
physical and mechanical properties, and/or the processability, for
example dispersing agents to achieve a uniform distribution of
particles, lubricants, plasticizers, antistatica, solvents, molding
agents, antioxidants, light stabilizers, fillers and reinforcing
fillers like glass balls and glass fibbers, silicates (e.g. mica,
clay, wollastonite), metal and semiconductor metal oxides, metal
carbonates, metal salts, metals and semiconductor metals, carbon
black, as powder, or carbon fibers, whiskers, metal and
semiconductor metal carbides, metal and semiconductor metal
nitrides, dyes, pigments and others.
[0203] The polymer compositions of the invention me be used in the
form of shaped articles.
[0204] The polymer composition or a polymerisable precursor
composition with host/guest particles may contain a solvent to
generate coating compositions. Suitable solvents are mentioned
before.
[0205] In another aspect of the invention the polymer composition
containing particles of the host/guest composition or particles
from polymers and dissolved host/guest chromophores may be used as
coatings on carrier materials, using the above mentioned
composition.
[0206] Another embodiment of the invention is a composition
comprising (a) a carrier material and (b) at least on one surface a
coating of a composition comprising (a) a polymer substrate, and
(b) particles of the composition, or particles from polymers and
dissolved host/guest chromophores, or both according to the
invention, homogeneously distributed therein.
[0207] In another aspect of the invention the composition
containing a polymer and soluble host/guest chromophores may be
used as coatings on carrier materials, using a solution of said
composition.
[0208] Another embodiment of the invention is a composition
comprising (a) a carrier material and (b) at least on one surface a
coating of a composition comprising (a) a polymer matrix, and (b) a
polymer and soluble host/guest chromophores according to the
invention, homogeneously distributed therein.
[0209] Suitable carrier materials may be selected from organic or
inorganic materials like glass, ceramics, minerals, plastics,
paper, wood, textiles, semiconductors, metals, metal oxides and
semiconductor metal oxides, and metal or semiconductor
metal-nitrides or -carbides.
[0210] The thickness of the coating depends on the desired use and
may be from 0.01 to 1000 .mu.m, preferably 0.05 to 500 .mu.m, and
especially preferred 0.1 to 100 .mu.m.
[0211] The coatings may be protected by covering coatings which
preferably are transparent. Such coatings are well known, in
particular photocrosslinked coatings are useful for this purpose,
and are well known in the art.
[0212] The coated materials are obtainable by known methods like
painting, casting or spincoating, directly or with dispersion of
the polymeric compositions.
[0213] It is also possible to use a polymerisable composition
containing polymer forming monomers or oligomeric precursors, in
particular crosslinkable olefinically unsaturated monomers are
useful in generating such coatings. The polymerization may be
induced thermally or by actinic radiation or both. It is often
preferred to carry-out the polymerisations in the presence of a
radical initiator species. The coating compositions are novel and a
further embodiment of the invention.
[0214] A further embodiment of the invention is a solvent
containing liquid composition, comprising
[0215] (1) a soluble polymer, and
[0216] (2) particles of the host and guest chromophore of a
composition according to the invention, or dissolved therein host
and guest chromophores according to the invention.
[0217] These compositions may contain a solvent, such as those
mentioned before, and optionally surfactants and dispersing agents.
The viscosity range of the composition depends on the desired
application, and can be readily by choice of solvent quantity,
polymers binder and fluorescent materials. To further achieve a
desired viscosity thickening agents may additionally be used.
Suitable solvents have been mentioned.
[0218] The preparation of this composition can be achieved by
simply mixing the ingredients together using suitable mixing
equipment. Dispersions are in general stable depending upon the
viscosity. Aggregated particles may be redistributed by
stirring.
[0219] In a highly advantageous embodiment of preparing coatings
polymerisable compositions can be used, wherein at least one
surface of a carrier material is coated and subsequently
polymerized by heat, radiation or both. Photopolymerizable mixtures
can also be used to generate fluorescent images by known
photoresist technology.
[0220] A further embodiment of the invention is a polymerisable
composition comprising polymerisable monomers or prepolymers in
admixture with a composition according to the invention in the form
of a powder containing particles, or with host and guest
chromophores according to the invention, preferably dissolved
therein, or both.
[0221] The composition may be used to generate the polymers or
polymer particles according to the invention as described before.
Preferably the composition contains a solvent, when coatings or
images are to be generated. The afore described embodiments also
apply to this composition, inclusive of the preferred
embodiments.
[0222] In a preferred embodiment the composition is based on
polymerisable monomers and/or prepolymers containing a group
selected from olefinically unsaturated groups, preferably from
--CH.dbd.CH.sub.2 and --C(CH.sub.3).dbd.CH.sub.2, which can be
thermally or photo-polymerized.
[0223] Photopolymerisable monomers and prepolymers are well known
in the art and described for example in EP-A-0 654 711. Preferred
photopolymerisable monomers and prepolymers are those based on the
esters or amides of acrylic acid or methacrylic acid and alcohols,
polyols, amines and polyamines.
[0224] Preferred ethylenically unsaturated photopolymerisable
agents are selected from the group of acrylic or methacrylic acid
esters of aliphatic, cycloaliphatic and cycloa(iphatic-aliphatic
alcohols and diols to tetrols, and amines and diamines to
tetramines containing especially preferred 2 to 12, and
particularly preferred 2 to 8 C-atoms. Some examples of these diols
are alkylenediols like ethylenglycol, 1,2- or 1,3-propanediol,
1,2-, 1,3- and 1,4-butanediol, pentanediol, hexanediol, octanediol,
decanediol, dodecanediol, cyclohexanediol,
di(hydroxymethyl)-cyclohexane, polyoxyalkylendiols from preferably
C.sub.2-C.sub.6alkylendiols with preferably 2 to 100 alkylenediol
units, more preferably 2 to 50 alkylenediol units, and most
preferably 2 to 20 alkylenediol units, like for example
polyethylenediols, polypolypropylenediols, polybutylenediols and
polyethylene/polypropylened- iols, further
1,1,1-trihydroxymethylethane or -propane, pentaerythritol and
dipentaerythritol. Some examples for polyamines are
ethylenediamine, 1,3- and 1,3-propanediamine, 1,2-, 1,3- and
1,4-butanediamine, 1,6-hexanediamine, diethylenetriamine,
triethylenetetramine, cyclohexanediamine,
(aminomethyl)cyclohexaneamine, isophorondiamine and
di(aminomethyl)cyclohexane. Examples of alcohols are linear or
branched C.sub.1 to C.sub.20alkanols.
[0225] The photopolymerisable composition may be particularly
suitable for generating coatings and images.
[0226] A further embodiment of the invention is a composition
comprising a carrier material with a high relief image of a
polymerized photoresist material, which contains a composition
according to the invention in the form of a powder containing
particles, or host and guest chromophores according to the
invention, or both, if desired dissolved and/or homogeneoulsly
distributed therein.
[0227] A further embodiment of the invention is a process for the
preparation of fluorescent high relief images on a carrier.
Preferably, this involves irradiating under a mask or by laser
writing, the above coated photopolymerisable composition (which
preferably has been dried and removed of solvent) on the carrier,
developing the irradiated composition and finally removing the
non-irradiated parts.
[0228] Removal of the non-irradiated parts in general is mostly
carried out by treatment with solvent.
[0229] All highly fluorescent materials described before can
broadly be used in optical and electrooptical devices.
[0230] A further embodiment of the invention is a process for the
creation of fluorescent radiation which requires the excitation
either electrically or by UV or visible radiation, or both, of a
fluorescent composition according to the invention.
[0231] Another embodiment of the invention is the use of the
compositions according to the invention as fluorescent
materials.
[0232] As described before benzo [4,5] imidazo [2,1-a]
isoindol-11-one, 1,2,3,4-tetrachloro-benzo [4,5] imidazo [2,1-a]
isoindol-11-one and some substituted derivatives are known in the
art. From our investigations it was found that benzo [4,5] imidazo
[2,1-a] isoindol-11-ones and 1,2,3,4-tetrachloro-benzo [4,5]
imidazo [2,1-a] isoindol-11-ones show very high light stabilities,
as measured by a time dependent exposure testing. Furthermore, it
was found that the light stability of these compounds is reduced by
substitution in the 7- and/or 8-positions. In the case of
1,2,3,4-tetraphenyl-benzo [4,5] imidazo [2,1-a] isoindol-11-one, it
exhibits a moderate light stability, which suffices for a number of
applications. However it was found, that the solid state
luminescence is maintained, the light stability is greatly
improved, and the compounds have a desired solubility, when the
benzo [4,5] imidazo [2,1-a] isoindol-11-one is substituted in the
1-, 2-, 3- and/or 4-positions and in the 7- and/or 8-positions with
selected substituents.
[0233] A further embodiment of the invention a compound of the
formula V, 9
[0234] wherein
[0235] at most three of R.sub.13, R.sub.14, R.sub.15 and R.sub.16
are H and at least one of R.sub.13, R.sub.14, R.sub.15 and R.sub.16
are a substituent selected from the group of C.sub.1 to
C.sub.18alkyl, C.sub.1 to C.sub.18alkoxy, C.sub.1 to
C.sub.18alkylthio, C.sub.1 to C.sub.12alkoxy-polyC.sub.2 to
C.sub.6oxyalkylene; unsubstituted or with F, Cl, Br, --CN, C.sub.1
to C.sub.12alkyl, C.sub.1 to C.sub.12alkoxy, C.sub.1 to
C.sub.12alkylthio, or-NR.sub.21R.sub.22 substituted C.sub.5 to
C.sub.8cycloalkyl, C.sub.5 to C.sub.8cycloalkoxy, C.sub.5 to
C.sub.8cycloalkylthio, C.sub.5 to C.sub.8cycloalkyl-C.sub.1 to
C.sub.4alkyl, C.sub.5 to C.sub.8cycloalkyl-C.sub.1 to
C.sub.4alkoxy, C.sub.5 to C.sub.8cycloalkyl-C.sub.1 to
C.sub.4alkylthio, phenyl, phenyloxy, phenylthio, phenyl-C.sub.1 to
C.sub.4alkyl, phenyl-C.sub.1 to C.sub.4alkoxy, phenyl-C.sub.1 to
C.sub.4alkylthio; or
[0236] R.sub.13 and R.sub.14 together, R.sub.15 and R.sub.16
together, or R.sub.13 and R.sub.14 together and R.sub.15 and
R.sub.16 together, or R.sub.14 and R.sub.15 together are selected
from the groups --CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd.CH- --,
--CH.dbd.CR.sub.24-CR.sub.25.dbd.N--,
--CH.dbd.N-CR.sub.25.dbd.CH--, --CH.dbd.CR.sub.24-N.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd.N--, --N.dbd.CR.sub.24-N.dbd.CH--,
--CH.dbd.CH-O--, --CH.dbd.CH-S--, --CH.dbd.CH-NR.sub.23--;
[0237] R.sub.17 and R.sub.20 independently from one another are H
or have the meaning of R.sub.18;
[0238] one of R.sub.18 and R.sub.19 are H and the other of R.sub.18
and R.sub.19 or both are a substituent selected from the group of
C.sub.1 to C.sub.18alkyl, C.sub.1 to C.sub.18alkoxy, C.sub.1 to
C.sub.18alkylthio, C.sub.1 to C.sub.12alkoxy-polyC.sub.2 to
C.sub.6-oxyalkylene; unsubstituted or with F, Cl, Br, --CN, C.sub.1
to C.sub.12alkyl, C.sub.1 to C.sub.12alkoxy, C.sub.1 to
C.sub.12alkylthio, or --NR.sub.21R.sub.22 substituted C.sub.5 to
C.sub.8cycloalkyl, C.sub.5 to C.sub.8cycloalkoxy, C.sub.5 to
C.sub.8cycloalkylthio, C.sub.5 to C.sub.8cycloalkyl-C.sub.1 to
C.sub.4alkyl, C.sub.5 to C.sub.8cycloalkyl-C.sub.1 to
C.sub.4alkoxy, C.sub.5 to C.sub.8cycloalkyl-C.sub.1 to
C.sub.4alkylthio, phenyl, phenyloxy, phenylthio, phenyl-C.sub.1 to
C.sub.4alkyl, phenyl-C.sub.1 to C.sub.4alkoxy, phenyl-C.sub.1 to
C.sub.4alkylthio, phenyl-C.sub.2 to C.sub.12alkylidene,
phenyl-C(O)--, phenyl-NR.sub.23-C(O)--,
phenyl-NR.sub.23-S(O).sub.2--, phenyl-S(O)--, phenyl-S(O).sub.2--,
phenyl-CO.sub.2--, phenyl-S(O)-O--, phenyl-SO.sub.3--,
phenyl-NR.sub.23--, or phenyl-CH.dbd.CH--; or
[0239] R.sub.17 and R.sub.18 together, R.sub.19 and R.sub.20
together, or R.sub.17 and R.sub.18 together and R.sub.19 and
R.sub.20 together, or R.sub.18 and R.sub.19 together are selected
from the groups --CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd.CH- --,
--CH.dbd.CR.sub.24-CR.sub.25.dbd.N--,
--CH.dbd.N-CR.sub.25.dbd.CH--, --CH.dbd.CR.sub.24-N.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd.N--, --N.dbd.CR.sub.24-N.dbd.CH--,
--CH.dbd.CH-O--, --CH.dbd.CH-S--, --CH.dbd.CH-NR.sub.23--;
[0240] R.sub.21 and R.sub.22 are independently from one another are
C.sub.1 to C.sub.20alkyl, phenyl, C.sub.1 to C.sub.12alkylphenyl,
benzyl or C.sub.1 to C.sub.12alkylbenzyl, or R.sub.21 and R.sub.22
together mean tetramethylene, pentamethylene or
--CH.sub.2CH.sub.2-O-CH.sub.2CH.sub.2--- ;
[0241] R.sub.23 is H C.sub.1 to C.sub.4alkyl or benzyl; and
[0242] R.sub.24 and R.sub.25 are independently from one another H,
C.sub.1 to C.sub.6alkyl, C.sub.1 to C.sub.6alkoxy, C.sub.1 to
C.sub.6alkylthio, or F, Cl or Br.
[0243] In a preferred embodiment R.sub.13 and R.sub.14 are
substituents, and most preferably R.sub.13, R.sub.14, R.sub.15 and
R.sub.16 are substituents. In still another preferred embodiment,
R.sub.13 and R.sub.14, R.sub.15 and R.sub.16, R.sub.14 and
R.sub.15, or R.sub.13 and R.sub.14 and R.sub.15 and R.sub.16 each
together mean --CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd.CH- --,
--CH.dbd.CR.sub.24-CR.sub.25.dbd.N--,
--CH.dbd.N-CR.sub.25.dbd.CH--, --CH.dbd.CR.sub.24-N.dbd.CH--.
[0244] In an other preferred embodiment R.sub.17 and R.sub.20 mean
H, and R.sub.17 and R.sub.18 or both are substituents. In still
another preferred embodiment, R.sub.17 and R.sub.18, R.sub.19 and
R.sub.20, R.sub.18 and R.sub.19, or R.sub.17 and R.sub.18 and
R.sub.19 and R.sub.20 each together mean
--CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--,
--N.dbd.CR.sub.24-CR.sub.25.dbd.CH--,
--CH.dbd.CR.sub.24-CR.sub.25.dbd.N-- -,
--CH.dbd.N-CR.sub.25.dbd.CH--, --CH.dbd.CR.sub.24-N.dbd.CH--.
[0245] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is alkyl, it maybe linear alkyl or
branched alkyl, and contain preferably 1 to 12 and more preferably
1 to 6 carbon atoms. Examples for alkyl have been given before.
Preferred alkyls are methyl, ethyl, n- or i-propyl, n-, I- and
t-butyl, and the isomers of pentyl and hexyl.
[0246] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is alkoxy, it maybe linear alkoxy
or branched alkoxy, and contain preferably 1 to 12 and more
preferably 1 to 6 carbon atoms. Examples for alkoxy have been given
before. Preferred alkoxies are methoxy, ethoxy, n- or i-propoxy,
n-, I- and t-buoxty, and the isomers of pentoxy and hexoxy.
[0247] In the context of the invention when one or more of
R.sub.13, R1.sub.4, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is alkylthiols, it maybe linear
alkylthiol or branched alkylthiol, and contain preferably 1 to 12
and more preferably 1 to 6 carbon atoms. Examples for alkylthio
have been given before. Preferred alkylthiols are methylthio,
ethylthio, n- or i-propylthio, n-, I- and t-butylthio, and the
isomers of pentylthio and hexylthio.
[0248] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is C.sub.1 to
C.sub.12alkoxy-polyC.sub.2 to C.sub.6oxyalkylene, the alkoxy maybe
linear alkoxy or branched alkoxy and contains preferably 1 to 6 and
more preferably 1 to 4 carbon atoms and may be for example methoxy,
ethoxy, propoxy and butoxy. The oxyalkylene group preferably
contains 2 to 4 and more preferably 2 or 3 carbon atoms and may be
ethylenoxy or 1,2-propylenoxy. The residue may contain 1 to 12,
preferably 1 to 6, and more preferably 1 to 4 repeating oxyalkylene
units.
[0249] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is cycloalkyl, it is preferably
cyclopentyl or cyclohexyl.
[0250] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is cycloalkoxy it is preferably
cyclopentoxy or cyclohexoxy.
[0251] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is cycloalkyltho it is preferably
cyclopentylthio or cyclohexylthio.
[0252] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is cycloalkyl-alkyl, the alkyl is
preferably ethyl and most preferably methyl, and the cycloalkyl is
preferably cyclopentyl or cyclohexyl. Preferred examples are
cyclopentylmethyl and cyclohexylmethyl.
[0253] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and is cycloalkyl-alkoxy, the alkoxy is
preferably ethoxy and most preferably methoxy, and the cycloalkyl
is preferably cyclopentyl or cyclohexyl. Preferred examples are
cyclopentyl-methoxy and cyclohexylmethoxy.
[0254] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 is cycloalkyl-alkylthio, the alkylthio is
preferably ethylthio and most preferably methylthio, and the
cycloalkyl is preferably cyclopentyl or cyclohexyl. Preferred
examples are cyclopentyl-methylthio and cyclohexylmethylthio.
[0255] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is phenylalkyl the alkyl group
preferably contains 1 or 2 carbon atoms and mostly preferred is
methyl. Especially preferred is benzyl.
[0256] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is phenylalkoxy, the alkoxy group
preferably contains 1 or 2 carbon atoms and mostly preferred is
methoxy. Especially preferred is benzyloxy.
[0257] In the context of the invention when one or more of
R.sub.13, R.sub.14, R.sub.15 and R.sub.16 as well as R.sub.17,
R.sub.18, R.sub.19 and R.sub.20 is phenylalkylthio, the alkylthio
group preferably contains 1 or 2 carbon atoms and mostly preferred
is methylthio. Especially preferred is benzylthio.
[0258] In the context of the invention when one or more of
R.sub.17, R.sub.18, R.sub.19 and R.sub.20 is phenyl-C.sub.2 to
C.sub.12-alkylidene, the alkylidene may be linear or branched and
may contain 2 to 6 and preferably 2 to 4 carbon atoms. Some
examples are ethylidene, 1,1- or 2,2-propylidene, and 1,1- or
2,2-butylidene.
[0259] Preferred substituents are F, Cl, C.sub.1 to C.sub.4alkyl,
C.sub.1 to C.sub.4alkoxy, C.sub.1 to C.sub.4alkylthio, and
--NR.sub.21R.sub.22, wherein R.sub.21 and R.sub.22 are
independently from one another is C.sub.1 to C.sub.12alkyl, phenyl
or benzyl.
[0260] In the context of the invention when R.sub.21 and R.sub.22
are alkyl it may be linear alkyl or branched alkyl and may contain
1 to 12 and preferably 1 to 6 carbon atoms.
[0261] In the context of the invention when R.sub.21 and R.sub.22
are alkylphenyl, the alkyl may be linear or branched and may
contain 1 to 8 and preferably 1 to 6 carbon atoms.
[0262] In the context of the invention when R.sub.21 and R.sub.22
are alkylbenzyl, the alkyl may be linear or branched and may
contain 1 to 8 and preferably 1 to 6 carbon atoms.
[0263] R.sub.23 is preferably H, methyl or ethyl.
[0264] In the context of the invention when R.sub.24 and R.sub.25
are alkyl, alkoxy, alkylthio may be linear or branched and may
contain 1 to 4 and preferably 1 or 2 carbon atoms.
[0265] In a preferred embodiment R.sub.13, R.sub.14, R.sub.15 and
R.sub.16 are preferably C.sub.1 to C.sub.4alkyl, C.sub.1 to
C.sub.4alkoxy, phenyl, or C.sub.1 to C.sub.4alkylphenyl. Mostly
preferred R.sub.13, R.sub.14, R.sub.15 and R.sub.16 are all
phenyl.
[0266] In still a further preferred embodiment R.sub.17 and
R.sub.20 are H, and R.sub.18 and R.sub.19 or both are C.sub.1 to
C.sub.18alkyl or C.sub.1 to C.sub.18alkoxy, or R.sub.17 and
R.sub.18, R.sub.19 and R.sub.20, R.sub.18 and R.sub.19, or R.sub.17
and R.sub.18 and R.sub.19 and R.sub.20 each together mean
--CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--, wherein R.sub.24 and
R.sub.25 mean independently from one another H, F, Cl, C.sub.1 to
C.sub.8alkyl or C.sub.1 to C.sub.8alkoxy.
[0267] In an especially preferred embodiment the compounds of
formula V correspond to formula VI, 10
[0268] wherein
[0269] R.sub.17 and R.sub.20 are H, and R.sub.18 and R.sub.19 or
both are C.sub.1 to C.sub.18alkyl or C.sub.1 to C.sub.18alkoxy, or
R.sub.18 and R.sub.19 together mean
--CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--; or R.sub.17 and R.sub.18
together or R.sub.19 and R.sub.20 together, or R.sub.17 and
R.sub.18 together and R.sub.19 and R.sub.20 together mean
--CH.dbd.CR.sub.24-CR.sub.25.dbd.CH--, wherein R.sub.24 and
R.sub.25 are independently from one another H, F, Cl, C.sub.1 to
C.sub.8alkyl or C.sub.1 to C.sub.8alkoxy. The alkyl is preferably
branched in the .alpha.- or .alpha.,.alpha.-position.
[0270] It was also found that 1,2,3,4-tetrachloro-benzo [4,5]
imidazo [2,1-a] isoindol-11-ones with branched alkyl substituents
possess a higher light stability than the methyl substituted
compounds, and that acyl substituted 1,2,3,4-tetrachloro-benzo
[4,5] imidazo [2,1-a] isoindol-11-ones have also a high light
stability and a desired solubility. A further embodiment of the
invention are compounds of the formula Via, 11
[0271] wherein
[0272] X.sub.1 is Cl or Br,
[0273] one of R'.sub.18 and R'.sub.19 or both are independently
from one another --COOH, or .alpha.- or .alpha.,.alpha. -branched
C.sub.3 to C.sub.20alkyl or Ra-C(O)--, wherein R.sub.a means
C.sub.1 to C.sub.20alkyl; or C.sub.5 to C.sub.8cycloalkyl, C.sub.5
to C.sub.8cycloalkyl-CH.sub.2--, phenyl, benzyl, which are
unsubstituted or substituted with halogen, C.sub.1 to C.sub.12alkyl
or C.sub.1 to C.sub.12alkoxy, or one of R'.sub.18 and R'.sub.19 is
.alpha.- or .alpha.,.alpha.-branched C.sub.3 to C.sub.20alkyl or
Ra-C(O)--, wherein R.sub.a means C.sub.1 to C.sub.20alkyl; or
C.sub.5 to C.sub.8cycloalkyl, C.sub.5 to
C.sub.8cycloalkyl-CH.sub.2--, phenyl, benzyl, which are
unsubstituted or substituted with halogen, C.sub.1 to C.sub.12alkyl
or C.sub.1 to C.sub.12alkoxy, and the other of R'.sub.18 and
R'.sub.19 is linear C.sub.1 to C.sub.12alkyl.
[0274] The branched alkyl is preferably selected from 1-methyl or
1,1-dimethyl substituted alk-1-yl. The alkyl preferably contains 3
to 18, more preferably 3 to 12, and most preferably 3 to 8 carbon
atoms. X.sub.1 is preferably Cl.
[0275] R.sub.a means preferably C.sub.3 to C.sub.12alkyl; or
cyclopentyl, cyclohexyl, phenyl, benzyl, which are unsubstituted or
substituted with F, Cl, Br, C.sub.1 to C.sub.6alkyl or C.sub.1 to
C.sub.6alkoxy.
[0276] In the context of the invention the linear alkyl contains
preferably 1 to 8, more preferably 1 to 6, and most preferably 1 to
4 carbon atoms.
[0277] Compounds of the formulae V, VI and VIa can be prepared in
analogy to known methods, e.g. described in EP-A 456 609, wherein
the preparation method is based on the following equation: 12
[0278] Usually the two isomers indicated above are obtained which
can be separated, if desired, e.g. by column chromatography. In
general, it is not necessary for the success of this invention to
separate the two structural isomers.
[0279] Another preferred embodiment of the present invention
relates to the use of the inventive compounds V, VI and VIa as
organic emitting materials in and for the preparation of
electroluminescence ("EL") devices. Those EL-devices are well known
in the art and e.g. described in U.S. Pat. No. 5,593,788, WO
94/15441, and the literature cited therein. For example one of the
common EL devices comprises two extremely thin layers (<1.0
.mu.m in combined thickness) which separate the anode and the
cathode. One layer specifically is chosen to inject and transport
holes and the other specifically chosen to inject and transport
electrons and also acting as the organic luminescent zone of the
device. The extremely thin organic luminescent medium offers
reduced resistance, permitting higher current densities for a given
level of electrical biasing. Since light emission is directly
related to current density through the organic luminescent medium,
the thin layers coupled with increased charge injection and
transport efficiencies have allowed acceptable light emission
levels (e.g. brightness levels capable of being visually detected
in ambient light) to be achieved with low voltages in ranges
compatible with integrated circuit drivers, such as transporting
layer also acting as the luminescent zone of the device.
[0280] In another preferred embodiment of this invention, the
inventive host/guest compositions can be used as organic emitting
material in a layer of an EL device as well as for the preparation
of such an EL device. Such devices are known in principle e.g. from
U.S. Pat. No. 5,593,788 and the prior art cited therein, hence, no
further details are necessary for a skilled person in the art.
[0281] Hence, electroluminescent devices comprising the inventive
compounds or compositions are also part of this invention. The
preparation of such devices is given in detail e.g. in the above
cited U.S. Pat. No. 5,593,788 or WO 94/15441.
[0282] The fluorescent composition of the present invention emits
solid state fluorescence with a greatly enhanced emission intensity
when compared to the solid-state emission intensity of a powder
that contains host units but lacks any guest units, or a powder
that contains guest units but lacks any host units.
[0283] The compositions on hand do show the following advantages
compared to known compositions:
[0284] a) a greatly enhanced and intense fluorescence emission is
generated,
[0285] b) an intense solid state fluorescence is imparted, wherein
the emission wavelengths are in the in the visible region of the
electromagnetic spectrum,
[0286] c) the composition can be excited using wavelengths in both
the UV and visible regions,
[0287] d) very good photostabilities and outdoor durabilities can
be achieved,
[0288] e) a wide range of emission wavelengths can be achieved
through selection of guest molecules (color tuning),
[0289] f) a high thermal stability can be achieved,
[0290] g) easy preparation for the materials i.e. co-precipitation
of the dissolved components is possible.
[0291] The following examples demonstrate the invention.
[0292] The designation of the benzo [4,5] imidazo [2,1-a]
isoindol-11-ones relies on the following formula: 13
[0293] A) Preparation of benzo [4,5]imidazo [2,1
-a]isoindol-11-ones.
EXAMPLE A1
[0294] 1,2,3,4-tetraphenyl-benzo [4,5] imidazo [2,1-a]
isoindol-11-one-7(or 8, A'1)-carboxylic acid (A1).
[0295] A 300 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 4.58 g (30.1 mmol) of
3,4-diaminobenzoic acid, 13.6 g (30.0 mmol) of
1,2,3,4-tetraphenylphthalic anhydride, and 100 ml of glacial acetic
acid. Under nitrogen atmosphere, the mixture is stirred and heated
at reflux for 5 hours. The slurry is cooled and the yellow solid is
isolated by filtration. The solid is washed with water and then
with methanol. 10.9 g of yellow solid is obtained (64%).
[0296] .sup.1H-NMR (CDCl.sub.3, TMS) : .delta.8.43 (d, J=1.2 Hz,
1H, H.sub.A'9 or H.sub.A'6), 8.33 (d, J=0.9 Hz, 1H, H.sub.A9 or
H.sub.A'6), 8.05 (dd, J=1.5, 8.4 Hz, 1H, H.sub.A7 or H.sub.A'8),
7.96 (dd, J=1.6, 8.5 Hz, 1H, H.sub.A7 or H.sub.A'8), 7.72 (d, J=8.3
Hz, 1H, H.sub.A6 or H.sub.A'9), 7.61 (d, J=8.5 Hz, 1H, H.sub.A6 or
H.sub.A'9), 7.30-7.24 (m, 8H), 7.18-7.15 (m, 2H), 6.92-6.89 (m, 6H)
6.81-6.76 (m, 4H).
EXAMPLE A2
[0297] 1,2,3,4-tetraphenyl-7-(t-butyl)-benzo [4,5] imidazo [2,1 -a]
isoindol-11-one (A2) and 1,2,3,4-tetraphenyl-8-(t-butyl)-benzo
[4,5] imidazo [2,1-a] isoindol-11-one (A'2).
[0298] A 100 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 0.99 g (6.01 mmol) of
4-(t-butyl)-o-phenylenedi- amine, 2.73 g (6.03 mmol) of
1,2,3,4-tetraphenylphthalic anhydride, and 15 ml of glacial acetic
acid. Under nitrogen atmosphere, the mixture is stirred and heated
at reflux for 3 hours. The slurry is cooled and the yellow solid is
isolated by filtration. The solid is washed with water. 2.5 g of
yellow solid is obtained (total 71%; 42% for A2 and 29% for A'2).
Two isomers can be separated by column chromatography using
CH.sub.2Cl.sub.2 as eluent.
[0299] A2 (7-position):
[0300] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.7.60 (d, J=1.3 Hz, 1
H, H.sub.6), 7.58 (d, J=8.4 Hz, 1 H, H.sub.9), 7.30 (dd, J=8.5, 1.4
Hz, 1H, H.sub.8), 7.30-7.16 (m, 10H), 6.87-6.83 (m, 6H), 6.81-6.76
(m, 4H), 1.29 (s, 9H).
[0301] .sup.13C-NMR(in CDCl.sub.3): .delta.160.3 (s, C=0), 156.1
(s, C.sub.4b), 149.6 (dt, C.sub.5a), 148.3 (m, C.sub.7), 147.9 (t,
C.sub.3), 145.5 (t, C.sub.2), 141.9 (t, C.sub.4 or C.sub.1), 138.4
(m), 138.1 (m), 137.7 (C.sub.4 or C.sub.1), 136.1 (m), 135.5 (m),
130.9, 130.8, 130.3, 130.1 (s), 129.8, 127.7, 127.5, 127.1, 127.0,
126.4, 126.3, 123.9 (dm, J.sup.1=160 Hz, C.sub.8), 118.7 (dd,
J.sub.1=160 Hz, C.sub.6), 111.6 (d, J.sup.1=170 Hz, C.sub.9), 35.0
(CMe.sub.3), 31.6 (CH.sub.3).
[0302] A'2 (8-position):
[0303] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.7.73 (d, J=1.6 Hz, 1
H, H.sub.9), 7.47 (d, J=8.6 Hz, 1 H, H.sub.6), 7.28-7.22 (m, 9H),
7.20-7.17 (m, 2H), 6.93-6.89 (m, 6H), 6.82-6.78 (m, 4H), 1.32 (s,
9H).
[0304] .sup.13C-NMR (CDCl.sub.3) : .delta.160.6 (s, C=0), 155.6 (s,
C.sub.2), 150.3 (m, C.sub.8), 147.9 (t, C.sub.3), 147.4 (ddd,
C.sub.5a), 145.4 (t, C.sub.2), 141.9 (t), 138.4 (m), 138.0 (m),
137.6 (t), 136.0 (m), 135.6 (m), 130.9, 130.8, 130.4, 130.2 (s),
129.8, 127.7, 127.5, 127.4, 127.1, 127.0, 126.3, 126.2, 122.4 (dd,
J.sup.1=160 Hz, C.sub.7), 121.1 (d, J.sup.1=160 Hz, C.sub.6), 109.3
(ddd, J.sup.1=160 Hz, C.sub.9), 35.2 (CMe.sub.3), 31.5
(CH.sub.3).
EXAMPLE A3
[0305] 1,2,3,4-tetraphenyl-benzo [4,5] imidazo [2,1-a]
isoindol-11-one (A3).
[0306] A 500 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 8.34 g (73.3 mmol) of
o-phenylenediamine (95%), 33.0 g (66.3 mmol) of
1,2,3,4-tetraphenylphthalic anhydride, and 200 ml of glacial acetic
acid. Under nitrogen atmosphere, the mixture is stirred and heated
at reflux for 11 hours. The slurry is cooled and the yellow solid
is isolated by filtration. The solid is washed with water and then
with methanol. 35.1 g of an yellow solid is obtained (92%).
[0307] .sup.1H-NMR (CDCl.sub.3, TMS) :.delta.7.66 (d, J=7.6 Hz,
1H), 7.55 (d, J=7.7 Hz, 1H), 7.30-7.15 (m, 12H), 6.93-6.88 (m, 6H),
6.81-6.76 (m, 4H).
[0308] MS: 524 ([M].sup.+).
EXAMPLE A4
[0309] 1,2,3,4-tetraphenyl-7(or 8)-nitro-benzo [4,5] imidazo
[2,1-a] isoindol-11-one (A4, A'4).
[0310] A 100 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 1.53 g (9.99 mmol) of
4-nitro-o-phenylenediamin- e, 4.53 g (10.0 mmol) of
1,2,3,4-tetraphenylphthalic anhydride, and 25 ml of glacial acetic
acid. Under nitrogen atmosphere, the mixture is stirred and heated
at reflux for 1.33 hours. The slurry is cooled and the yellow solid
is isolated by filtration. The solid is washed with water and then
with methanol. 6.1 g of a pale yellow solid is obtained.(100%).
[0311] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.8.57 (d, J=2.2 Hz, 1H,
H.sub.A9 or H.sub.A'6), 8.48 (d, J=2.1 Hz, 1H, H.sub.A9 or
H.sub.A'6), 8.22 (dd, J=2.1, 8.8 Hz, 1H, H.sub.A7 or H.sub.A'8),
8.13 (dd, 1H, H.sub.A7 or H.sub.A'8), 7.75 (d, J=8.8 Hz, 1H,
H.sub.A6 or H.sub.A'9), 7.65 (d, J=8.9 Hz, 1H, H.sub.A6 or
H.sub.A'9), 7.32-7.23 (m, 8H), 7.18-7.15 (m, 2H), 6.95-6.90 (m,
6H), 6.81-6.76 (m, 4H).
[0312] MS: 569 ([M].sup.+).
EXAMPLE A5
[0313] 1,2,3,4-tetraphenyl-7(or 8)-methyl-benzo [4,5] imidazo
[2,1-a] isoindol-11-one (A5, A'5).
[0314] A 100 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 1.30 g (10.64 mmol) of
4-methyl-o-phenylenediam- ine, 4.53 g (10.01 mmol) of
1,2,3,4-tetraphenylphthalic anhydride, and 25 ml of glacial acetic
acid. Under nitrogen atmosphere, the mixture is stirred and heated
at reflux for 5 hours. The slurry is cooled and the yellow solid is
isolated by filtration. The solid is washed with water and MeOH.
4.16 g of a yellow solid is obtained (77%).
[0315] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.7.52 (d, J=8.1 Hz, 1H,
H.sub.A6 or H.sub.A'9), 7.48 (br s, 1H, H.sub.A9 or H.sub.A'6),
7.42 (d, J=8.2 Hz, 1H, H.sub.A6 or H.sub.A'9), 7.36 (br s, 1H,
H.sub.A9 or H.sub.A'6), 7.27-7.23 (m, 8H), 7.18-7.15 (m, 2H), 7.06
(br d, 1H, H.sub.A7 or H.sub.A'8), 6.99 (br d, 1H, H.sub.A7 or
H.sub.A'8), 6.92-6.88 (m, 6H), 6.80-6.75 (m, 4H).
[0316] MS: 538 ([M].sup.+), 537 ([M-H].sup.+).
EXAMPLE A6
[0317] 1,2,3,4-tetraphenyl-7(or 8)-methoxy-benzo [4,5] imidazo
[2,1-a] isoindol-11-one (A6, A'5).
[0318] A 100 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 1.38 g (9.99 mmol) of
4-methoxy-o-phenylenediam- ine, 4.52 g (9.99 mmol) of
1,2,3,4-tetraphenylphthalic anhydride, and 20 ml of glacial acetic
acid. Under nitrogen atmosphere, the mixture is stirred and heated
at reflux for 7 hours. The slurry is cooled and the yellow solid is
isolated by filtration. The solid is washed with water, followed by
purification with column chromatography. 3.75 g of yellow solid is
obtained (68%).
[0319] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.7.52 (d, J=8.6 Hz, 1H,
H.sub.A6 or H.sub.A'9), 7.42 (d, J=8.9 Hz, 1H, H.sub.A6 or
H.sub.A'9), 7.27-7.23 (m, 8H), 7.20 (d, J=2.6 Hz, 1H, H.sub.A9 or
H.sub.A'6), 7.19-7.14 (m, 2H), 7.08 (d, J=2.4 Hz, 1H, H.sub.A9 or
H.sub.A'6), 6.92-6.88 (m, 6H), 6.85 (dd, 1H, J=2.4, 8.7 Hz,
H.sub.A7 or H.sub.A'8), 6.80-6.74 (m, 1H, H.sub.A7 or
H.sub.A'8+4H).
[0320] MS: 554 ([M].sup.+).
EXAMPLE A7
[0321] 1,2,3,4-tetraphenyl-6,7-8,9-dibenzo-benzo [4,5] imidazo
[2,1-a] isoindol-11-one (A7).
[0322] A 100 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 0.84 g (4.03 mmol) of
9,10-diaminophenanthrene, 1.83 g (4.04 mmol) of
1,2,3,4-tetraphenylphthalic anhydride, and 15 ml of glacial acetic
acid. Under nitrogen atmosphere, the mixture is stirred and heated
at reflux for 5 hours. The slurry is cooled and the orange solid is
isolated by filtration. The solid is washed with water and MeOH,
followed by purification with column chromatography. 2.01 g of an
orange solid is obtained (80%).
[0323] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.9.19 (dd, J=1.5, 8.0
Hz, 1H, H.sub.9 or H.sub.10), 8.70 (dd, J=7.8 Hz, 1H, H.sub.9 or
H.sub.10), 8.64 (m, 1H, H.sub.6 or H.sub.13), 8.32 (m, 1H, H.sub.6
or H.sub.13), 7.64-7.59 (m, 4H, H.sub.7,8,11,12), 7.37-7.28 (m,
8H), 7.25-7.22 (m, 2H), 6.96-6.90 (m, 6H), 6.86-6.79 (m, 4H).
EXAMPLE A8
[0324] 1,2,3,4-tetrachloro-7(or 8)-nitro-benzo [4,5] imidazo [2,1
-a] isoindol-11-one (A8, A'8).
[0325] A 200 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 2.30 g (15.0 mmol) of
4-nitro-o-phenylenediamin- e, 4.29 g (15.0 mmol) of
1,2,3,4-tetrachlorophthalic anhydride, and 60 ml of glacial acetic
acid. Under nitrogen atmosphere, the mixture is stirred and heated
at reflux for 2 hours. The slurry is cooled and the pale yellow
solid is isolated by filtration. The solid is washed with water and
MeOH. 5.48 g of a pale yellow solid is obtained (91%).
[0326] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.8.75 (dd, J=1.7 Hz,
1H, H.sub.A9 or H.sub.A'6), 8.74 (dd, J=2.3 Hz, 1H, H.sub.A9 or
H.sub.A'6), 8.40 (dd, J=2.2, 8.8 Hz, 1H, H.sub.A7 or H.sub.A'8),
8.32 (dd, J=2.3, 8.9 Hz, 1H, H.sub.A7 or H.sub.A'8), 7.97 (dd,
J=8.7 Hz, 1 H, H.sub.A6 or H.sub.A'9), 7.96 (dd, J=9.0 Hz, 1 H,
H.sub.A6 or H.sub.A'9).
[0327] MS: 403 ([M+2].sup.+), 401 ([M].sup.+) .
EXAMPLE A9
[0328] 1,2,3,4-tetrachloro-benzo [4,5] imidazo [2,1-a]
isoindol-11-one-7(or 8)-carboxylic acid (A9, A'9).
[0329] A 1 l round-bottom flask equipped with a stirrer and reflux
condenser is charged with 15.2 g (100 mmol) of 3,4-diaminobenzoic
acid, 28.6 g ( 100 mmol) of tetrachlorophthalic anhydride, and 450
ml of glacial acetic acid. Under nitrogen atmosphere, the mixture
is stirred and heated at reflux for 15 hours. The slurry is cooled
and the greenish yellow solid is isolated by filtration. The solid
is washed with water and methanol. 37.0 g of a greenish yellow
solid is obtained (92%).
[0330] MS: 404 ([M+4]+), 402 ([M+2]+), 400 ([M]+), 387 ([M+4-OH]+),
385 ([M+2-OH]+), 383 ([M-OH]+).
EXAMPLE A10
[0331] 1,2,3,4-tetrachloro-7(or 8)-(t-butyl)-benzo [4,5] imidazo
[2,1-a] isoindol-11-one (A10, A'10).
[0332] A 100 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 2.48 g (15.1 mmol) of
4-(2'-methyl-2'-propyl)-o- -phenylenediamine, 4.30 g (15.0 mmol) of
tetrachlorophthalic anhydride, and 40 ml of glacial acetic acid.
Under nitrogen atmosphere, the mixture is stirred and heated at
reflux for 3.5 hours. The slurry is cooled and the yellow solid is
isolated by filtration. The solid is washed with water and
methanol. 5.22 g of a yellow solid is obtained (84%).
[0333] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.7.82 (dd, J=0.5, 1.8
Hz, 1H, H.sub.A9 or H.sub.A'6), 7.73 (dd, J=0.5, 8.6 Hz, 1H,
H.sub.A6 or H.sub.A'9), 7.42 (dd, J=1.8, 8.6 Hz, 1 H, H.sub.A7 or
H.sub.A'8), 1.40 (s, 9H).
[0334] MS: 416 ([M+4]+), 414 ([M+2]+), 412 ([M]+), 401
([M+4-CH3]+), 399 ([M+2-CH3]+), 397 ([M-cu3]+).
EXAMPLE A11
[0335] 1,2,3,4-tetrachloro-7(or 8)-benzoyl-benzo [4,5] imidazo
[2,1-a] isoindol-11-one (A11, A'11).
[0336] A 100 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 2.13 g (10.0 mmol) of
3,4-diaminobenzophenone, 2.87 g (10.0 mmol) of tetrachlorophthalic
anhydride, and 23 ml of glacial acetic acid. Under nitrogen
atmosphere, the mixture is stirred and heated at reflux for 3.5
hours. The slurry is cooled and the yellow solid is isolated by
filtration. The solid is washed with water and methanol, followed
by dissolving in hot CHCl.sub.3 with a soxhlet extractor to remove
insoluble impurities. After condensation, 3.36 g of a yellow solid
is obtained (72%).
[0337] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.8.28 (dd, 1H, H.sub.A9
or H.sub.A'6), 7.93 (dd, J=0.7, 8.5 Hz, 1H, H.sub.A6 or H.sub.A'9),
7.87-7.82 (m, 3H, H.sub.A7 or H.sub.A'8, and H2', 6'), 7.64 (tt.
J=1.2, 7.5 Hz, 1H, H.sub.3',5'), 7.52 (t, J=7.6 Hz. 2H,
H.sub.4').
[0338] MS: 464 ([M+4].sup.+), 462 ([M+2].sup.+), 460 ([M].sup.+),
387 ([M+4-C.sub.6H.sub.5].sup.+), 385 ([M+2-C.sub.6H.sub.5].sup.+),
383 ([M-C.sub.6H.sub.5].sup.+), 359 ([M+4-C.sub.6H.sub.5CO].sup.+),
357 ([M+2-C.sub.6H.sub.5CO].sup.+), 355
([M-C.sub.6H.sub.5CO].sup.+).
EXAMPLE A12
[0339] 1,2,3,4-tetrachloro-benzo [4,5] imidazo [2,1-a]
isoindol-11-one (A12).
[0340] Compound A12 is prepared according to the procedure
described in EP-A-0 456 609.
[0341] B) Preparation of Quest Chromophores
EXAMPLE B1
[0342] N,N'-dibenzyl-quinacridone (B1).
[0343] A 500 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 3.13 g (10.0 mmol) of quinacridone
(hereinafter referred to QA), 17.11 g (100 mmol) of benzyl bromide,
138.21 g (1.00 mol) of K.sub.2CO.sub.3 and 200 ml of
dimethylformamide (DMF). Under a nitrogen atmosphere, the mixture
is stirred and heated at reflux for 7.5 hours. The slurry is cooled
and the orange solid is isolated by filtration. The solid is washed
with water. acetone and ethanol. There yields 4.34 g of an orange
solid (88%).
[0344] .sup.1H-NMR (DMSO-d.sub.6, Dimethylsulfoxide(DMSO)):
.delta.8.56 (s, 2H, H.sub.1), 8.35 (dd, J=7.9 Hz, 2H, H.sub.5),
7.79 (dt, J=8.2 Hz, 2H, H.sub.4), 7.67(d, J=8.6 Hz, 2H, H.sub.2),
7.37 (t, 4H, H.sub.3), 7.33 (t, 2H, H.sub.6), 7.31 (t, 2H,
H.sub.7), 7.27 (d, 4H, H.sub.8), 5.29 (s, 4H, H.sub.9).
EXAMPLE B2
[0345] N,N'-dibenzyl-diphenyl-diketopyrrolopyrrol
[0346] A 100 ml round-bottom flask equipped with a stirrer and
reflux condenser is charged with 1.47 g (5.1 mmol) of
diphenyl-diketopyrrolopyrr- ole (hereinafter referred to DPP), 3.44
g (20.1 mmol) of benzyl bromide, 1.38 g (10.0 mmol) of
K.sub.2CO.sub.3 and 50 ml of DMF. Under nitrogen atmosphere, the
mixture is stirred and heated at 100.degree. C. for 42.5 hours. The
slurry is cooled and the orange solid is isolated by filtration.
The solid is washed with water and MeOH, followed by dissolving in
hot CHCl.sub.3. This CHCl.sub.3 solution is applied to silica gel
column using CH.sub.2Cl.sub.2 as eluent. After condensation, 1.21 g
of an orange solid is obtained (51%).
[0347] .sup.1H-NMR (CDCl.sub.3, TMS): .delta.7.75 (d, J=7.1 Hz, 4H,
H.sub.1), 7.49-7.43 (m, 6H, H.sub.2 and H.sub.3), 7.30 (t, J=7.4 Hz
4H H.sub.5) 7.24 (t, J=7.3 Hz, 2H, H.sub.6), 7.19 (d, J=7.4 Hz, 4H,
H.sub.4), 4.99 (s, 4H, H.sub.7).
[0348] MS: 468 ([M]+).
[0349] C) Preparation of Fluorescent Compositions
EXAMPLE C1
[0350] 1.0.times.10.sup.-4 mol (0.0557 g) of A1 as a host compound
and various amounts of Rhodamine 19 (Kodak Laboratory Chemicals) as
a guest compound (B3) or Rhodamine 6G (Kodak Laboratory Chemicals)
as a guest compound (B4) are dissolved in 20 ml of
1,2-dichloroethane and mixed. The solvent is then evaporated using
a rotary evaporator (RE47, Yamato Scientific Co., LTD.) to obtain
fluorescent powders including A1 and B3 or B4 of various
concentrations.
[0351] Photoluminescence spectra of the fluorescent powders are
measured using a fluorescence spectrophotometer in standard
reflection mode (F-4500, HITACHI Co., LTD.) with a solid sample
holder by exciting the host compound at absorption band thereof
with monochromic light (.lambda..sub.max=360 nm). The results are
listed in Table 1.
1TABLE 1 Fluorescent properties of fluorescent powders Guest
concentration Photoluminescence spectrum Host Guest (mol %) Peak
wavelength (nm) Peak intensity A1 none 0 512 545 A1 B3 0.1 571 987
A1 B3 0.2 573 1040 A1 B3 0.5 580 869 A1 B4 0.2 579 968
EXAMPLE C2
[0352] 1.0.times.10.sup.-4 mol (0.0557 g) of A1 and various amounts
of B1 are dissolved in 20 ml of 1,2-dichloroethane and mixed. The
solvent is then sublimed by freeze-drying with a freeze-dryer
(FD81. Tokyo Rikakikai Co., LTD.) to obtain fluorescent powders
including A1 and B1 of various concentrations. Photoluminescence
spectra of the fluorescent powders are measured in the same manner
as in Example C1. The results are listed in Table 2.
2TABLE 2 Fluorescent properties of fluorescent powders including A1
and B1 Guest concentration Photoluminescence spectrum Host Guest
(mol %) Peak wavelength (nm) Peak intensity A1 none 0 510 570 A1 B1
0.1 563 687 A1 B1 0.2 565 1014 A1 B1 0.5 564 964
EXAMPLE C3
[0353] 3.0.times.10.sup.-4 mol (0.1706 g) of A2 or A'2 as a host
compound and various amounts of B1 or B2 as a guest compound are
dissolved in 20 ml of 1-methyl-2-pyrrolidone and mixed. The
solution is then poured into 400 ml of water which is vigorously
stirred with a homogenizer (ULTRA-TURRAX T25. IKA-Labortechnik). A
precipitate is filtered and dried in vacuo at 60.degree. C. to
obtain fluorescent powders including A2 or A3 and B1 or B2 of
various concentrations. Photoluminescence spectra of the
fluorescent powders are measured in the same manner as in Example
C1. The results are listed in Tables 3 and 4.
3TABLE 3 Fluorescent properties of fluorescent powders including A2
and B1 or B2 Guest concentration Photoluminescence spectrum Host
Guest (mol %) Peak wavelength (nm) Peak intensity A2 none 0 526 197
A2 B1 0.2 523 1155 A2 B1 0.5 524 2005 A2 B1 1.0 526 2555 A2 B1 2.0
528 2876 A2 B1 5.0 529 1579 A2 B2 1.0 534 2054 A2 B2 2.0 537 2324
A2 B2 5.0 542 2160
[0354]
4TABLE 4 Fluorescent properties of fluorescent powders including
A'2 and B1 of Guest concentration Photoluminescence spectrum Host
Guest (mol %) Peak wavelength (nm) Peak intensity A'2 none 0 522
552 A'2 B1 1.0 524 2854 A'2 B1 2.0 525 3942 A'2 B1 5.0 529 2227
EXAMPLE C4
[0355] Carefully measured amounts of A1 as a host compound, B1 as a
guest compound and an acrylic polymer (PMMA;
polymethylmethacrylate, Aldrich Chemical Co. Inc.) are dissolved in
CHCl.sub.3/methanol (95/5 vol. %) (Wako Chemical Co. Ltd.), to
yield a clear, homogeneous solution (5wt % concentration). The
mixture is then cast onto a glass substrate using a wire bar (KCC
rod No. 8, RK Print-Coat Instruments) and the solvent removed. At
this point the polymer film has the visual color and spectroscopic
features typical of the precursor. Photoluminescence spectra of the
fluorescent films are measured in the same manner as in Example C1.
The results are listed in Table 5.
5TABLE 5 Fluorescent properties of the polymer films A1 B1 PMMA
Photoluminescence spectrum (wt %) (wt %) (wt %) Peak wavelength
(nm) Peak intensity 5 0 95 501 401 5 0.05 95 545 561 5 0.1 95 548
564 5 0.2 95 552 586 5 0.3 95 555 788 10 0 90 501 440 10 0.05 90
546 593 10 0.1 90 551 819 10 0.2 90 553 811 10 0.3 90 559 896 30 0
70 501 461 30 0.05 70 551 621 30 0.1 70 552 781 30 0.2 70 556 734
30 0.3 70 558 799
EXAMPLE C5
[0356] 0.1 g of the fluorescent powder of Example C3, which
includes A2 as host and B2 as guest, is dispersed in 1.0 g of a
functional acrylate monomer [KAYARAD D310 (Nippon Kayaku Co.)]
using a homogenizer (ULTRA-TURRAX T25. IKA-Labortechnik). 5.0 g of
a 10 wt % of polyvinyalcohol (PVA-117, Kurare) aqueous solution is
added over the period of about 10 minutes to the vigorously stirred
dispersion to give an uniform suspension, and recrystallized
K.sub.2S.sub.2O.sub.8 as initiator is added at room temperature.
The reaction mixture is removed of oxygen by bubbling with N.sub.2
gas for approximately 30 minutes, then placed in a temperature
controlled water bath at 80.degree. C. for 10 hours. Highly
cross-linked polymer particles containing fluorescent powder are
obtained and isolated by filtration. The particles are then washed
oftentimes with water and methanol. Drying is performed in a vacuum
oven at 60.degree. C. overnight. Yield 34.4%. Photoluminescence
spectra of the fluorescent polymer particles are measured in the
same manner as described in Example C1. The results are listed in
Table 6.
6TABLE 6 Fluorescent properties of fluorescent polymer powders.
Guest concentration Photoluminescence spectrum Host Guest (mol %)
Peak wavelength (nm) Peak intensity A2 none 0 525 370 A2 B2 5.0 538
1520
EXAMPLE C6
[0357] 0.1 g of A2 as host, none or 0.002 g of B2 as guest and 1.0
g of a functional acrylate monomer (KAYARAD D310) are dissolved in
10 ml of 1-methyl-2-pyrrolidone. The solution is then poured
dropwise into 200 ml of 2 wt % of polyvinyalcohol (PVA-117, Kurare)
aqueous solution which is vigorously stirred with a homogenizer. A
yellow precipitate with green fluorescence is immediately
generated, to which the recrystallized initiator
K.sub.2S.sub.2O.sub.8 is added. The reaction mixture is removed of
oxygen by bubbling through N.sub.2 gas for approximately 30
minutes, and placed in a temperature controlled water bath at
80.degree. C. for 10 hours. Highly crosslinked polymer particles
are obtained and isolated by filtration. The particles are then
washed oftentimes with water and methanol. Drying is performed in a
vacuum oven at 60.degree. C. overnight. Yield 42.5%.
Photoluminescence spectra of the fluorescent polymer particles are
measured in the same manner as described in Example C1. The results
are listed in Table 7.
7TABLE 7 Fluorescent properties of fluorescent polymer powders.
Guest concentration Photoluminescence spectrum Host Guest (wt %)
Peak wavelength (nm) Peak intensity A2 none 0 524 410 A2 B2 2.0 531
1790
EXAMPLE C7
[0358] To an all glass reaction flask fitted with a rubber seal,
magnetic stirrer, and maintained under a nitrogen atmosphere, 30 ml
of degassed water is charged and heated to 60.degree. C.
Maintaining the reaction temperature of 60.degree. C., a degassed
slurry of 2.08 g (20 wt %) A12, 5.12 g (49 wt %) ethylene glycol
dimethacrylate, 3.1 g (30 wt %) methyl methacrylate, none or 0.103
g (1 wt %) Lumogen F Orange (BASF), 0.16 g 2,2'-
Azobis(isobutyronitrile) and 10 ml chloroform are added in a single
addition. The vigorously stirred reaction is allowed to proceed for
6 hours, and then the reaction mixture is filtered. The precipitate
consists of bright orange particles, that are non-uniform in shape
and size. These particles are washed with water several times and
dried at the water aspirator. Final drying is performed in a vacuum
oven at 60.degree. C. overnight. Yield 90%. The polymer powder thus
obtained is ground into a fine powder, via a standard laboratory
mortar and pestle. Photoluminescence spectra of the fluorescent
polymer powders are measured in the same manner as described in
Example C1. The results are listed in Table 8.
8TABLE 8 Fluorescent properties of fluorescent polymer powders.
Guest Photoluminescence spectrum concentration Peak Host Guest (wt
%) wavelength (nm) Peak intensity A12 none 0 511 242 A12 Lumogen F
1.0 584 680 Orange
EXAMPLE C8
[0359] Light stability of 1,2,3,4-tetraphenyl-benzo [4,5] imidazo
[2,1-a] isoindol-11-ones.
[0360] 1,2,3,4-tetraphenyl-7(or 8)-methoxy-benzo [4,5] imidazo
[2,1-a] isoindol-11-one and various derivatives are charged in the
sample holder used in Example C1. The samples are exposed to light
with a Xenon lamp weather-ometer (WEL-15X-HC-B.Ec, Suga Test
Instruments Co.) for 100 hours under the following conditions:
9 light intensity 0.35 W/cm.sup.2 at 340 nm, temperature 63.degree.
C. at black panel, humidity 50%.
[0361] The intensity of the photoluminescence is measured prior to
light exposure and the intensity loss in percent is measured after
100 hours of light exposure as described in example C1, comparing
the peak heights. The results are summarized in table 9.
10TABLE 9 Light stability of stability of
1,2,3,4-tetraphenyl-benzo[4,5]imidazo[2,1-a] isoindol-11-ones
.lambda..sub.max Intensity prior Intensity after Loss Compound (nm)
to exposure exposure (%) A3 505 1211 759 37 A2 517 810 751 7 A'2
505 2033 1595 22 A5 533 488 390 20 A6 556 45 45 <1 A7 598 159
152 4
EXAMPLE C9
[0362] Light stability of 1,2,3,4-tetrachloro-7-methyl-benzo [4,5]
imidazo [2,1-a] isoindol-11-one and other derivatives.
[0363] The procedure of example C8 is repeated but this time using
1,2,3,4-tetrachloro-7-methylbenzo [4,5] imidazo [2,1-a]
isoindol-11-one (A") as comparison with
1,2,3,4-tetrachloro-7-t-butyl-benzo [4,5] imidazo [2,1-a]
isoindol-11-one (A10) and 1,2,3,4-tetrachloro-7-benzoylbenzo [4,5]
imidazo [2,1-a] isoindol-11-one (A11). The results are summarized
in table 10.
11TABLE 10 Intensity prior to Intensity after Compound
.lambda..sub.max (nm) exposure exposure Loss (%) A" 534 170 142 17
A10 546 156 136 11 A11 524 273 247 10
* * * * *