Fluorescent chromophore, covalently linked to an organic support material

A composition comprising a solid organic support material to which are either directly, or via a bridging group, covalently linked fluorescent chromophores, characterized in that the chromophores are selected from the group consisting of benzo[4,5]imidazo[2,1-a]isoindol-11-ones.

The instant invention relates to a composition comprising a solid organic 
support material to which are either directly, or via a bridging group, 
covalently linked fluorescent chromophores, characterized in that the 
chromophores are selected from the group consisting of 
benzo[4,5]imidazo[2,1-a]isoindol-11-ones. 
Further, the present invention concerns a process for the preparation of 
the inventive composition and its use as fluorescent material. 
Over many years the concept of preparing fluorescent materials by 
covalently attaching a fluorescent moieties to a polymer backbone is one 
that has been studied by a number of scientists. For example, Y. Morishima 
et.al. (Chemistry Letters pp 1149, 1989) covalently attached rhodamine B 
moieties to a polymer backbone, whilst H-U. Siegmund (Ad. Mater. 3(12), 
605 (1991)) successfully attached coumarin type structures to a polymer. 
In all cases the fluorescent moiety attached can be classified as a dye 
molecule. Typically, dye molecules in the condensed state possess only 
little or no fluorescence at all. It is only upon dilution, preferably to 
the molecular state, when the material impart or display increased 
fluorescence. The phenomena of a molecule losing fluorescence in the 
condensed state is termed concentration quenching, and has been widely 
documented in the literature. 
Correspondingly, if one prepares polymers with large weight percentage of a 
fluorescent moiety attached, there will come a point where the material 
ceases to fluoresce or only possess weak fluorescence. 
F. W. Harris et.al. (ACS Symp. Ser. 132, 39 (1980)) prepared the compound 
1,2,3,4-tetraphenyl-benzo[4,5]imidazo[2,1-a]isoindol-11-one as a model 
material for their investigations into phenylated polyimidazopyrrolones, 
for potential use in aerospace applications. However, in their paper they 
made no reference to its fluorescence behavior and gave no hints to the 
possibility of preparing the derivatives herein described, that could be 
readily polymerized and impart photo stability. 
The solid-state fluorescent compound 
1,2,3,4-tetrachloro-benzo[4,5]imidazo[2,1-a]isoindol-11-one, and its 
derivatives, are disclosed in EP-A 456 609. The (insoluble) pigments are 
bright yellow in color, which impart intense solid-state fluorescence and 
display unprecedented photostabilies for a fluorescent material. 
Hence, the object of the present invention was to provide a composition 
with excellent solid-state fluorescence and practical solubilities on the 
base of derivatives of benzo[4,5]imidazo[2,1-a]isoindol-11-ones, 
preferably tetraphenyl derivatives thereof, which are covalently linked to 
a solid organic support material. Particularly, novel soluble molecules 
and monomers that readily facilitate themselves to undergo fluorescent 
composition forming reaction should be provided. Further, another object 
was to provide homo- and copolymers which possess high weight percent 
ratios of the corresponding monomer unit, carrying the chromophore, 
without compromising the fluorescent intensity, that is no or only a 
negligible loss in fluorescence intensity with increasing the weight 
concentration of chromophore moiety on the polymer should be obtained. 
Further objects were to provide a composition where 
a) an intense solution and solid-state (non-crystalline) fluorescence is 
present in the visible region, 
b) very excellent photostabilities can be achieved, 
c) high thermal stabilities are achieved, 
d) soluble and insoluble fluorescent compositions can be generated, 
e) migration of the fluorescent molecules is essentially excluded, 
f) a high lightfastness is achieved, and 
g) an easy preparation for the materials, like single pot reactions is 
possible. 
Accordingly, a composition comprising a solid organic support material to 
which are either directly, or via a bridging group, covalently linked 
fluorescent chromophores, characterized in that the chromophores are 
selected from the group consisting of 
benzo[4,5]imidazo[2,1-a]isoindol-11-ones was found. 
In addition, a process for the preparation of the inventive composition and 
its use as fluorescent material were found, too. Therefore, the first 
embodiment of the present relates to a composition comprising a solid 
organic support material to which are either directly, or via a bridging 
group, covalently linked fluorescent chromophores, characterized in that 
the chromophores are selected from the group consisting of 
benzo[4,5]imidazo[2,1-a]isoindol-11-ones. 
In a preferred embodiment of the present invention the support material is 
selected from the group consisting of linear or crosslinked polymers with 
the pendent chromophores, and surface modified polymers containing pendent 
chromophores on their surfaces. 
A further preferred embodiment of the present invention concerns a 
completion form (A), namely polymers with chromophore molecules, which are 
either directly or via a bridging group covalently linked to the polymer 
backbone. 
A further preferred embodiment of the present invention concerns a 
completion form (B), namely organic support materials to which chromophore 
molecules are either directly, or via a bridging group, covalently linked 
on the surface of the said support materials. 
The following description relates to completion form (B), which as compared 
to the completion form (A) possesses the further advantage of reducing the 
consumption of chromophore molecules, arising from the fact that the 
chromophore molecules are not located in the interior of a polymer 
particle. 
When applying completion form (B), the organic support material can be 
opaque, translucent or transparent, preferably transparent. Suitable 
support materials are for example thermosetting, thermoplastic or 
structurally crosslinked plastics. The support materials contain 
functional groups on the surface for the linking of the chromophore 
molecules. The surface groups may be obtained by a plasma treatment in a 
reactive gaseous atmosphere. Preferred support materials are glasses and 
plastics, for example plastics with functional groups. 
The functional groups of the organic support material are preferably 
selected from the group consisting of amino-, hydroxyl-, thiol-, 
carboxyl-, SO.sub.3 H-groups or isocyanate groups. The organic support 
material may be a polymer that has had its surface modified, for example 
by plasma treatment, or it may be a natural or synthetic polymer prepared 
from monomers containing functional groups. Synthetic polymers may also be 
emulsion polymers and latices comprising at least one monomer having 
functional groups. Examples for natural polymers are polysaccharides like 
cellulose, starch or chitosane, which may be partially etherified by 
C.sub.1 -C.sub.4 alkyl or esterified with C.sub.1 -C.sub.8 -acyl. 
Synthetic polymers with functional groups are known and can be prepared by 
well known methods. Some examples for synthetic polymers are 
polyvinylalcohol and copolymers of vinyl alcohol with unsubstituted or 
substituted olefines as comonomers; polymethacrylic acid, polyacrylic acid 
and polymaleic acid and copolymers of methacrylic acid, acrylic acid 
and/or maleic acid with unsubstituted or substituted olefines as 
comonomers; polyhydroxyalkylacrylates, polyhydroxyalkylmethacrylates and 
polymaleic acid hydroxyalkylesters, and copolymers of hydroxyalkylesters 
of methacrylic acid, acrylic acid and/or maleic acid with unsubstituted or 
substituted olefins as comonomers; polyacrylamide and polymethacrylamide 
and copolymers of acryl amide, methacrylamide or both with unsubstituted 
or substituted olefins as comonomers; polyaminoalkylacrylates, 
-methacrylates and -maleic acid esters and copolymers of 
aminoalkylacrylates, -methacrylates, -maleic acid esters or two or three 
of these with unsubstituted or substituted olefins as comonomers; 
polyhydroxyalkyl- or polyaminoalkylvinylalcohol and copolymers of 
hydroxyalkylvinylether, aminoalkylvinylether or both with unsubstituted or 
substituted olefins as comonomers; hydroxylated polybutadienes from 
butadiene, isoprene or chloroprene and copolymers of butadiene, isoprene, 
chloroprene or two or three of these monomers with unsubstituted or 
substituted olefins as comonomers; hydroxy- or aminopolystyrene, 
chlormethylpolystyrene, and polystyrenesulfonic acid and copolymers of 
hydroxystyrene, aminostyrene, chloromethylstyrene, polystyrenesulfonic 
acid, or two or more of these monomers with unsubstituted or substituted 
olefins as comonomers; polyglycidyl ethers and hydroxyalkylated or 
aminoalkylated polyglycidyl ethers; and polyesters, polyamides and 
polyurethanes from hydroxyl containing monomers. The support material may 
also be composed of thermosetting resins, for example epoxy resins, 
melamine-formaldehyde resins and phenol-formaldehyde resins. Suitable 
olefinic comonomers are for example ethene, propene, butene, pentene, 
octene, vinylchloride, vinylidenechloride, styrenes and acrylonitrile. The 
support material may also be composed of crosslinked polymers, for example 
polymerisates with functionalized olefins, optionally nonfunctionalized 
olefinic monomers, and diolefinic monomers like butadiene, divinylbenzene 
or diol-diacrylates or diol-dimethacrylates, whereby the olefins may be 
selected from the above mentioned functional group containing olefins. 
Further suitable vinyl polymers are polyvinylpyrrolidone, 
polyvinylimidazole and polyvinylpyridine and copolymers of 
vinylpyrrolidone, vinylimidazole, vinylpyridine or two or three of them 
with unsubstituted or substituted olefins as comonomers. 
The polymers may be block polymers, alternating polymers, graft polymers or 
random polymers. 
In another preferred embodiment of this invention, the composition 
according to the invention is a solid-state fluorescent composition in the 
form of particles whereby fluorescent chromophores, selected from 
benzo[4,5]imidazo[2,1 -a]isoindol-11-ones are covalently linked either 
directly or through a bridging group to the surface of the particles. 
The particles may have an average diameter of 50 nm to 1000 .mu.m, 
preferably 0.1 to 500 .mu.m, more preferably 0.1 to 200 .mu.m, most 
preferably 0.1 to 100 .mu.m, and especially preferred 5 to 50 .mu.m. The 
particles may be round shaped or irregularly shaped, depending on the 
manufacturing process, and the particles may be compact or porous. 
The organic support material may for example be a shaped article from 
polymers, and the like. The size and shape of the article is arbitrary and 
depends on its final use. These shaped articles are a further object of 
the invention. The surface of the support material for a shaped article my 
be smooth or porous. The shaped articles include any composite structures. 
A weight average molecular weight of the polymer of the present invention 
can be in the range from 10.sup.3 to 2.times.10.sup.6, preferably, 
10.sup.4 to 10.sup.6, more preferably, 2.times.10.sup.4 to 10.sup.6, and 
most preferably 4.times.10.sup.4 to 5.times.10.sup.5 gmol.sup.-1, as 
determined by gel permeation chromatography, using polystyrene standards 
as calibration. 
The amount of chromophores is preferably from 0.00001 to 5, more preferably 
0.001 to 5, more preferably 0.001 to 3, and most preferably 0.001 to 2 
percent by weight, with respect to the total weight of the composition. 
The fluorescent chromophore is advantageously covalently linked to the 
supporting material through a bridging group. The bridging group may 
contain 1 to 60 atoms, preferably 1 to 30 atoms, and particularly 
preferred 1 to 20 atoms, selected from the group consisting of C, O, S and 
N. The bridging group especially preferred is a hydrocarbon residue, which 
may be interrupted with one or more and/or end-capped with one of the 
heteroatoms selected from the group consisting of O, S, N or the group 
C(O), and which preferably contains in total from 1 to 40 atoms, more 
preferably 2 to 30 atoms and especially preferred 3 to 20 atoms. 
The fluorescent chromophore covalently linked either directly or through a 
bridging group to the surface of the support material m ay be represented 
by formula I, 
EQU -X.sub.1 -(R.sub.1).sub.r -(X.sub.2).sub.s -R.sub.3 - Chromophore (I) 
wherein 
X.sub.1 and X.sub.2 each independently from one another means a direct 
bond, or X.sub.1 and X.sub.2 each independently from one another mean -O-, 
-S-, -NR.sub.2 -, -C(O)-O-, -O-C(O)-, -O-C(O)-O-, -SO.sub.2 -O-, 
-O-SO.sub.2 -, -O-SO.sub.2 -O-, -NR.sub.2 -C(O)-, -C(O)-NR.sub.2 -, 
-NR.sub.2 -C(O)-O-, O-C(O)-NR.sub.2 -, -NR.sub.2 -C(O)-NR.sub.2 -, 
-NR.sub.2 -SO.sub.2 -, -SO.sub.2 -NR.sub.2 -, -NR.sub.2 -SO.sub.2 -O-, 
O-SO.sub.2 -NR.sub.2 - or -NR.sub.2 -SO.sub.2 -NR.sub.2 - each R.sub.1 
independently from one another means a bivalent bridging group, 
Chromophore stands f or the monovalent molecule, 
R.sub.2 each independently from one another is H, C.sub.1 -C.sub.12 alkyl, 
C.sub.5 - or C.sub.6 cycloalkyl, C.sub.5 - or C.sub.6 cycloalkylmethyl or 
-ethyl, phenyl, benzyl or 1-phenyl-2-ethyl, 
R.sub.3 each independently from one another are a direct bond, C.sub.1 
-C.sub.18 alkylene, C.sub.5 - or C.sub.6 cycloalkylene, C.sub.6 -C.sub.10 
arylene or C.sub.7 -C.sub.12 aralkylene, 
r means the numbers 0 or 1 and s means the numbers 0 or 1, with the proviso 
that s is 0, if r is 0, and 
x means the numbers 0 or 1 and y means the numbers 0 or 1, with the proviso 
that y is 0, if x is 0. 
In the context of alkyl, R.sub.2 is preferably 1 to 6 and especially 
preferred 1 to 4 C-atoms. Some examples are methyl, ethyl, n- or i-propyl, 
butyl, pentyl, hexyl and octyl. In the context of cycloalkyl R.sub.2 is 
preferably cyclohexyl, and in the context of cycloalkylmethyl 
cyclohexylmethyl in a preferred embodiment R.sub.2 means H or C.sub.1 
-C.sub.4 alkyl. The bivalent bridging group is preferably a hydrocarbon 
residue, which preferably contains 1 to 30, more preferably 2 to 20, most 
preferably 3 to 20 and particularly preferred 3 to 18 C-atoms, which is 
unsubstituted or one or more times substituted with C.sub.1 -C.sub.4 
alkyl, C.sub.1 -C.sub.4 alkoxy or .dbd.O. The hydrocarbon residue may be 
also one or more times interrupted with heteroatoms selected from the 
group consisting of -O-, -S- and -NR.sub.2 -, whereby R.sub.2 is 
preferably H or C.sub.1 -C.sub.4 alkyl. 
The bivalent bridging group can be C.sub.1 -C.sub.20 -, preferably C.sub.2 
-C.sub.12 alkylene, which may be linear or branched. Some examples are 
methylene, ethylene, 1,2- or 1,3-propylene, 1,2-, 1,3- or 1,4-butylene, 
pentylene, hexylene, octylene, dodecylene, tetradecylene, hexadecylene and 
octadecylene. 
The bivalent bridging group can be polyoxyalkylene with 2 to 12, preferably 
2 to 6 and more preferably 2 to 4 oxyalkylene units and 2 to 4, preferably 
2 or 3 C-atoms in the alkylene moiety. Especially preferred is 
polyoxyethylene and polyoxypropylene with 2 to 6 oxyalkylene units. 
The bivalent bridging group may be C.sub.5 -C.sub.12, preferably C.sub.5 
-C.sub.8 - and most preferably C.sub.5 or C.sub.6 -cycloalkylene like for 
example cyclopentylene, cyclohexylene, cyclooctylene or cyclododecylene. 
The bivalent bridging group may be C.sub.5 -C.sub.12 -, preferably C.sub.5 
-C.sub.8 - and more preferably C.sub.5 - or C.sub.6 -cycloalkyl-C.sub.1 
-C.sub.12 -alkylene and most preferably C.sub.5 - or C.sub.6- 
cycloalkyl-C.sub.1 -C.sub.4 -alkylene. Some examples are 
-cyclopentyl-C.sub.n H.sub.2n - and -cyclohexyl-C.sub.n H.sub.2n -, 
wherein n means a number of 1 to 4. Especially preferred is 
-cyclohexyl-CH.sub.2 -. 
The bivalent bridging group may be C.sub.5 -C.sub.12 -, preferably C.sub.5 
-C.sub.8 - and more preferably C.sub.5 - or C.sub.6 -cycloalkane-(C.sub.1 
-C.sub.12 alkylene).sub.2 - and most preferably -(C.sub.1 -C.sub.4 
-alkylene).sub.2. Some examples are cyclopentane-(C.sub.n H.sub.2n 
-).sub.2 and cyclohexane-(C.sub.n H.sub.2n -).sub.2, wherein n means a 
number of 1 to 4. Especially preferred is -CH.sub.2 -cyclohexane-CH.sub.2 
-. 
The bivalent bridging group may be C.sub.6 -C.sub.14 arylene and preferably 
C.sub.6 -C.sub.10 arylene, for example naphthylene or more preferably 
phenylene. The bivalent bridging group may be C.sub.7 -C.sub.20 aralkylene 
and preferably C.sub.7 -C.sub.12 aralkylene. More preferred is 
arylene-C.sub.n H.sub.2n -, wherein arylene means naphthylene and 
preferably phenylene, and n means a number from 1 to 4. Examples are 
benzylene and phenylethylene. 
The bivalent bridging group may be arene-(C.sub.n H.sub.2n -).sub.2 -, 
wherein arene is preferably naphthalene and more preferably benzene and n 
is a number from 1 to 4. Examples are xylene and benzene(CH.sub.2 
CH.sub.2).sub.2 -. 
R.sub.3 contains as alkylene preferably 1 to 12 and more preferably 1 to 6 
C-atoms. Especially preferred examples are methylene, ethylene, 1,2- or 
1,3-propylene and 1,2-, 1,3- and 1,4-butylene. R.sub.3 means as arylene 
preferably phenylene and as aralkylene preferably benzylene. 
In a preferred embodiment the bridging group may be selected from the 
formula Ia 
EQU --C(O)--O--R'--O--C(O)--(R")-- (Ia), 
wherein R' is C.sub.2 to C.sub.20, preferably C.sub.2 to C.sub.12, and more 
preferably C.sub.2 to C.sub.6 alkylene, phenylene, benzylene, or 
oligoxyalkylene with preferably 2 to 6, and more preferably 2 to 4 
oxyethylene and/or oxypropylene units, and R" means a direct bond, C.sub.1 
to C.sub.12 alkylene, phenylene or benzylene. 
The chromophores in formula I inventively are selected from the group of 
consisting of derivatives of benzo[4,5]imidazo[2,1-a]isoindol-11-one. 
The monovalent chromophore residues in formula I may be unsubstituted or 
substituted with F, Cl, Br, I, -CN, -NO.sub.2, C.sub.1 to C.sub.18 alkyl, 
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.18 
aryl-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.5 to C.sub.17 heteroaralkyl-SO- or 
-SO.sub.2, tertiary amino with 3 to 30 carbon atoms, and alkoxyalkyl with 
2 to 20 carbon atoms. 
The cyclic aliphatic and aromatic residues (substituents) may be also 
substituted, for example with F, Cl, Br, I, -CN, -NO.sub.2, C.sub.1 to 
C.sub.18 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.6 to C.sub.18 aryl, 
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.1 alkyloxy, C.sub.3 to 
C.sub.12 cycloalkyloxy, C.sub.6 to C.sub.18 aryloxy. The substituent alkyl 
may be linear or branched and may be substituted with a halogen like F or 
Cl. 
Examples of 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. 
The number of substituents is arbitrary and depends essentially upon 
synthetic possibilities and the desired optical properties pertaining to 
fluorescence and absorption. 
The benzo[4,5]imidazo[2,1-a]isoindol-11-ones used in completion form (B) 
are preferably monovalent residues and may be selected from the formulae 
II and IIa, 
##STR1## 
wherein 
neighboring carbon atoms of the benzene rings can be condensed with benzene 
rings, heteroaromatic rings or both, and to these rings can be linked to a 
free bond rather than benzene rings of the core polycyclic structure, 
moreover, the aromatic rings are unsubstituted or substituted with F, Cl 
or Br, I, -CN, -NO.sub.2, C.sub.1 to C.sub.18 alkyl, 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.18 aryl-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.5 to C.sub.17 heteroaralkyl-SO- or -SO.sub.2, tertiary 
amino with 3 to 30 carbon atoms, and alkoxyalkyl with 2 to 20 carbon 
atoms. 
The cyclic aliphatic and aromatic residues may be also substituted, for 
example with F, Cl, Br, I, -CN, -NO.sub.2, C.sub.1 to C.sub.18 alkyl, 
C.sub.3 to C.sub.12 cycloalkyl, C.sub.6 to C.sub.18 aryl, 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.1 alkyloxy, C.sub.3 to C.sub.12 
cycloalkyloxy, C.sub.6 to C.sub.18 aryloxy. The cyclic aliphatic and 
aromatic residues (substituents) may be also substituted, for example with 
halogens like F, Cl or Br; or -CN, -NO.sub.2, C.sub.1 to C.sub.18 alkyl, 
C.sub.3 to C.sub.12 cycloalkyl, C.sub.6 to C.sub.18 aryl, , 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.1 alkyloxy, C.sub.3 to C.sub.12 
cycloalkyloxy, C.sub.6 to C.sub.18 aryloxy. The substituent alkyl may be 
linear or branched and may be substituted with halogen like F or Cl. 
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. 
Preferably 1 or 2 rings are condensed with the neighboring carbon atoms to 
form bicyclic or tricyclic systems. They may be selected from benzene, 
furan, thiophene, pyrrole, pyridine, and pyrimidine. 
In a preferred embodiment the monovalent fluorescent residues correspond to 
formulae IIb and IIc, 
##STR2## 
wherein 
R.sub.01, R.sub.02, R.sub.03, R.sub.04, and R.sub.05 independently from one 
another mean H, Cl, C.sub.1 to C.sub.18 alkyl, C.sub.1 to C.sub.18 alkoxy, 
phenyl, benzyl, C.sub.1 to C.sub.12 alkylphenyl or C.sub.1 to C.sub.12 
alkylbenzyl. R.sub.05 in formula IIc means preferably H. 
Some preferred examples of solid-state fluorescent chromophores 
corresponding to formula I are 
##STR3## 
The composition according to completion form B may be prepared according to 
well known immobilization methods. A further object of the invention is a 
process for the preparation of the composition according to completion 
form B, characterized in that a organic support material, containing 
functional groups on the surface, is reacted with functionalized 
fluorescent chromophores. 
The reaction may be carried-out by dissolving the functional chromophore 
compound in an inert solvent, adding a support material and reacting the 
mixture at suitable temperatures, for example 0 to 200.degree. C. and 
preferably 20 to 150.degree. C. Suitable solvents are described later. The 
isolation is carried-out by known filtration methods, and the material may 
be purified by washing, and finally it may be dried. 
The immobilization and the synthesis of bridging groups can be carried out 
according to methods well known in the art and are well documented in the 
literature. In principle it is possible to covert one functional group 
into another functional group, for example -CH.sub.2 OH-- groups through 
oxidation into carboxylic acids, carboxylic acids in amides or carboxylic 
acids into halogenides, amine groups into isocyanate groups, alcohols or 
amines into carbonates or urethanes. It is also possible, to react 
alcohols or amines with halogen carboxylic acids (for example monochloro 
acetic acid or chloromethylbenzoic acid which may then be linked to 
hydroxyl or amino groups). It is further possible to carry out chain 
extensions with di-functional agents like epoxides, azirines, diols, 
diamines, dicarboxylic acids or -esters and diisocyanates. Reactions using 
di-functional agents can be single-step or multi-step, depending on the 
degree of chain length desired. The bridging groups may be introduced 
through the functional groups of the support material or the functional 
groups of the chromophore molecule. 
A further preferred embodiment this invention concerns completion form (A), 
according to which the inventive composition comprises as a support 
material a polymer backbone to which are either directly or via a bridging 
groups the fluorescent molecules are covalently linked. 
The preparation of polymers and their immobilization is well known in the 
art. In principle there may be used two procedures. In a first aspect it 
is possible to polymerize monomers with pendent chromophore molecules. In 
a second aspect it is possible to use polymers with pendent functional 
groups and to react them with chromophore molecules containing functional 
groups. 
For the fluorescent compounds, as well as the bridging groups, the 
accomplishments and preferred embodiments described for completion form 
(B) are to be considered to apply to completion form (A). 
The designated fluorescent compounds are linked through functional groups 
bonded to structural units of the backbone. Examples of functional groups 
are -OH, -SH, -NH.sub.2, -NHR.sub.2, -CH.dbd.O, carboxylic acid, -SO.sub.3 
H, epoxide, vinyl or isocyanate, wherein R.sub.2 is preferably H or 
C.sub.1 to C.sub.4 alkyl. 
The polymers can be selected from natural or synthetic polymers. Examples 
of natural polymers are polysaccharides like cellulose, starch or 
chitosane, which may be partially etherified by C.sub.1 -C.sub.4 alkyl or 
esterified with C.sub.1 -C.sub.8 acyl. Synthetic polymers with functional 
groups can be prepared in accordance with well known methods. 
Some examples of synthetic polymers are polyvinylalcohol and copolymers of 
vinyl alcohol with unsubstituted or substituted olefines as comonomers; 
polymethacrylic acid, polyacrylic acid and polymaleic acid and copolymers 
of methacrylic acid, acrylic acid and/or maleic acid with unsubstituted or 
substituted olefines as comonomers; polyhydroxyalkylacrylates, 
polyhydroxyalkylmethacrylates and polymaleic acid hydroxyalkylesters, and 
copolymers of hydroxyalkylesters of methacrylic acid, acrylic acid and/or 
maleic acid with unsubstituted or substituted olefins as comonomers; 
polyacrylamide and polymethacrylamide and copolymers of acryl amide, 
methacrylamide or both with unsubstituted or substituted olefins as 
comonomers; polyaminoalkylacrylates, -methacrylates and -maleic acid 
esters and copolymers of aminoalkylacrylates, -methacrylates, -maleic acid 
esters or two or three of these with unsubstituted or substituted olefins 
as comonomers; polyhydroxyalkyl- or polyaminoalkylvinylalcohol and 
copolymers of hydroxyalkylvinylether, aminoalkylvinylether or both with 
unsubstituted or substituted olefins as comonomers; hydroxylated 
polybutadienes from butadiene, isoprene or chloroprene and copolymers of 
butadiene, isoprene, chloroprene or two or three of these monomers with 
unsubstituted or substituted olefins as comonomers; hydroxy- or 
aminopolystyrene, chlormethylpolystyrene, and polystyrenesulfonic acid and 
copolymers of hydroxystyrene, aminostyrene, chloromethylstyrene, 
polystyrenesulfonic acid, or two or more of these monomers with 
unsubstituted or substituted olefins as comonomers; polyglycidyl ethers 
and hydroxyalkylated or aminoalkylated polyglycidyl ethers; and 
polyesters, polyamides and polyurethanes from hydroxylic group containing 
monomers. The polymer may also be composed of thermosetting resins, for 
example epoxide resins, melamine-formaldehyde resins and 
phenol-formaldehyde resins. Suitable olefinic comonomers are for example 
ethene, propene, butene, pentene, octene, vinylchloride, 
vinylidenechloride, styrenes and acrylonitrile. Further suitable vinyl 
polymers are polyvinylpyrrolidone, polyvinylimidazole and 
polyvinylpyridine and copolymers of vinylpyrrolidone, vinylimidazole, 
vinylpyridine or two or three of them together with unsubstituted or 
substituted olefins as comonomers. 
The polymer may also be composed of crosslinked polymers, for example 
polymerisates with functionalized olefins, optionally nonfunctionalized 
olefinic monomers, and di-olefinic monomers like butadiene, divinylbenzene 
or dioldiacrylates or dioldimethacrylates, whereby the olefins may be 
selected from the above mentioned functional group containing olefins. 
Particularly, thermosetting resins are preferred which are selected from 
the group consisting of epoxide resins, melamine-formaldehyde resins and 
phenol-formaldehyde resins. 
The weight average molecular weight of the polymer of the present invention 
usually is chosen in the range from 10.sup.3 to 2.times.10.sup.6, 
preferably from 10.sup.4 to 10.sup.6, more preferably from 
2.times.10.sup.4 to 10.sup.6, and most preferably from 4.times.10.sup.4 to 
5.times.10.sup.5 gmol.sup.-1, preferably determined by gel permeation 
chromatography, using polystyrene standards as a calibration. 
The weight ratio of chromophore structural units to non-fluorescent 
structural units is dependent on the actual practical application, hence 
there are no well defined preferred ratios, other than the broad range 
100:0 to 1:999. In certain applications where both color strength and 
fluorescence are required, then the preferred ratios of chromophore 
structural units to non-fluorescent structural units are 20:80 to 100:0, 
preferably 50:50 to 100:0 and more preferably 80:20 to 100:0. In 
circumstances where fluorescence is desired but color strength is not 
required, then the preferred ratio of chromophore structural units to 
non-fluorescent structural units are 20:80 to 1:999, more preferably 10:90 
to 1:999 and more preferably 5:95 to 1:999. 
In one embodiment of the polymeric composition of the invention and as a 
further object of the invention the polymer can be in the form of 
particles, which may be obtained by milling polymers or by emulsion 
polymerizations. The particles may have an average diameter of 50 nm to 
1000 .mu.m, preferably 0.1 to 500 .mu.m, more preferably 0.1 to 200 .mu.m, 
most preferably 0.1 to 100 .mu.m, and especially preferred 5 to 50 .mu.m. 
The particles may be round shaped or irregularly shaped, depending on the 
manufacturing process, and the particles may be compact or porous. 
The polymer may be composed from monomeric units with covalently linked 
monovalent and/or divalent residues of a selected chromophore (the polymer 
may optionally contain other co-momomeric units); 
##STR4## 
or may be composed of recurring crosslinkable units of formula IIIa alone 
or in combination with one or both of the structural units of formulae III 
and IIIa, 
##STR5## 
wherein 
A and A.sub.1 are trivalent organic residues, 
Chromophore means ,either directly or via a bridging group, a covalently 
linked monovalent fluorescent chromophore defined before, 
whereby A is copolymerizable with A.sub.1 when used in combination. 
The polymer may additionally contain structural units of formula IIIa, 
EQU --A.sub.2 -- (IIIb), 
wherein A.sub.2 means the same or a different divalent residue from the 
same group of A. 
A, A.sub.1 and A.sub.2 may be derived from monomers selected from the group 
consisting of olefins, polyalcohols (preferably diols or triols), 
polyamines (preferably diamines and triamines), polyisocyanates 
(preferably di- or tri-isocyanates), carboxylic (preferably di- or 
tricarboxylic acids) acids and polyepoxides (preferably di- or 
triepoxides). 
The weight ratio of structural elements of formula III, IIIa, or IIIb, 
resp., to non-fluorescent structural units is dependent on the actual 
practical application, hence there are no well defined preferred ratios, 
other than the broad range 100:0 to 1:999. In certain applications where 
both color strength and fluorescence are required, then the preferred 
ratios of chromophore structural units to non-fluorescent structural units 
is 20:80 to 100:0, preferably 50:50 to 100:0 and more preferably 80:20 to 
100:0. In circumstances where fluorescence is desired but color strength 
is not required, then the preferred ratio of chromophore structural units 
to non-fluorescent structural units is 20:80 to 1:999, more preferably 
10:90 to 1:999 and more preferably 5:95 to 1:999. 
In a preferred embodiment the polymers according to the invention contain 
recurring structural units of formula IV, recurring structural units of 
formula IVa, and optionally recurring structural units of formula V, 
##STR6## 
wherein 
X.sub.1 and X.sub.2 each independently of one another mean a direct bond, 
or X.sub.1 and X.sub.2 each independently of one another mean -O-, -S-, 
-NR.sub.2 -, -C(O)-O-, -O-C(O)-, -O-C(O)-O-, -SO.sub.2 -O-, -O-SO.sub.2 -, 
-O-SO.sub.2 -O-, -NR.sub.2 -C(O)-, -C(O)-NR.sub.2 -, -NR.sub.2 -C(O)-O-, 
O-C(O)-NR.sub.2 -, -NR.sub.2 -C(O)-NR.sub.2 -, -NR.sub.2 -SO.sub.2 -, 
-SO.sub.2 -NR.sub.2 -, -NR.sub.2 -SO.sub.2 -O-, -O-SO.sub.2 -NR.sub.2 - or 
-NR.sub.2 -SO.sub.2 -NR.sub.2 -, 
R.sub.1 means a bivalent bridging group, 
chromophore means a monovalent fluorescent moiety, 
R.sub.2 means H, C.sub.1 -C.sub.12 alkyl, C.sub.5 - or C.sub.6 cycloalkyl, 
C.sub.5 - or C.sub.6 cycloalkylmethyl or -ethyl, phenyl, benzyl or 
1-phenyl-2-ethyl, 
R.sub.3 means a direct bond, C.sub.1 -C.sub.18 alkylene, C.sub.5 - or 
C.sub.6 -cycloalkylene, C.sub.6 -C.sub.10 arylene or C.sub.7 -C.sub.12 
aralkylene, 
the r each independently of one another mean the numbers 0 or 1 and the s 
each independently of one another mean the numbers 0 or 1, with the 
proviso that if s is 0, r is 0, 
R.sub.4 and R.sub.5 each independently of one another mean H, C.sub.1 
-C.sub.6 alkyl, C.sub.6 -C.sub.10 aryl or C.sub.7 -C.sub.12 aralkyl, 
R.sub.6 means H or the group -C(O)O-R.sub.11, 
R.sub.7 means H, C.sub.1 -C.sub.6 alkyl, C.sub.6 -C.sub.10 aryl or C.sub.7 
-C.sub.12 aralkyl, 
R.sub.8 means H, F, Cl, CN, C.sub.1 -C.sub.6 alkyl or C.sub.6 -C.sub.10 
aryl, 
R.sub.9 means H, C.sub.1 -C.sub.6 alkyl or -C(O)O-R.sub.11, 
R.sub.10 means H, C.sub.1 -C.sub.6 alkyl, C.sub.6 -C.sub.10 aryl, C.sub.7 
-C.sub.12 aralkyl, imidazolyl, pyrrolidonyl, F, Cl, CN or the group 
-X.sub.1 -(R.sub.1).sub.r -(X.sub.2).sub.s -H, and 
R.sub.11 means H, K, Na, C.sub.1 -C.sub.18 alkyl, C.sub.1 -C.sub.18 
hydroxyalkyl, cyclohexyl, cyclopentyl, cyclohexylmethyl, phenyl, C.sub.1 
-C.sub.4 alkylphenyl, benzyl or C.sub.1 -C.sub.4 alkylbenzyl. 
For X.sub.1, X.sub.2, R.sub.1, R.sub.2, R.sub.3, r, s, and Chromophore the 
meanings and preferred embodiments as described for completion form (B) 
also pertain to completion form (A). 
R.sub.4 and R.sub.5 mean as alkyl preferably C.sub.1 -C.sub.4 alkyl, for 
example methyl, ethyl, n- or i-propyl and n-, i- or t-butyl, as aryl 
preferably naphthyl or phenyl, and as aralkyl preferably benzyl. 
Especially preferred R.sub.4 is H and R.sub.5 is H or methyl. 
R.sub.6 means preferably H, -C(O)OH or -C(O)O-C.sub.1 to C.sub.4 -alkyl. 
R.sub.7 means as alkyl preferably C.sub.1 to C.sub.4 alkyl, for example 
methyl, ethyl, n- or i-propyl, and n-, i- or t-butyl; as aryl preferably 
naphthyl or phenyl and as aralkyl preferably benzyl. Especially preferred 
R.sub.7 is H. 
R.sub.8 for alkyl means is preferably C.sub.1 to C.sub.4 alkyl, for example 
methyl, ethyl, n- or i-propyl and n-, i- or t-butyl, and for aryl it is 
preferably phenyl or naphthyl. Especially preferred R.sub.8 is H, Cl, CN, 
phenyl or C.sub.1 to C.sub.4 alkyl. 
R.sub.9 means as alkyl preferably C.sub.1 -C.sub.4 alkyl, for example 
methyl, ethyl, n- or i-propyl and n-, i- or t-butyl. In the group 
-C(O)O-R.sub.11, R.sub.11 means preferably H or C.sub.1 -C.sub.12 alkyl, 
more preferably C.sub.1 -C.sub.6 alkyl, like for example methyl, ethyl, 
propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, 
dodecyl, tetradecyl, hexadecyl and octadecyl. Especially preferred R.sub.9 
is H, -C(O)OH or -C(O)-O-C.sub.1 -C.sub.4 alkyl. 
R.sub.10 means as alkyl preferably C.sub.1 -C.sub.4 alkyl, for example 
methyl, ethyl, n- or i-propyl and n-, i- or t-butyl, as aryl preferably 
phenyl and naphthyl, and as aralkyl preferably benzyl. R.sub.10 means 
preferably H, C.sub.1 -C.sub.4 alkyl, phenyl, pyrrolidonyl, F, Cl, CN or 
the group -X.sub.1 -(R.sub.1).sub.r -(X.sub.2).sub.s -H. 
R.sub.11 may be for example H, K, Na, C.sub.1 -C.sub.6 alkyl, C.sub.1 
-C.sub.6 -hydroxyalkyl, cyclohexyl, cyclopentyl, cyclohexylmethyl, phenyl, 
methylphenyl, benzyl or methylbenzyl. 
The weight ratio of structural elements of formula IV to non-fluorescent 
structural units is dependent on the actual practical application, hence 
there are no well defined preferred ratios, other than the broad range 
100:0 to 1:999. In certain applications where both color strength and 
fluorescence are required, then the preferred ratios of chromophore 
structural units to non-fluorescent structural units is 20:80 to 100:0, 
preferably 50:50 to 100:0 and more preferably 80:20 to 100:0. In 
circumstances where fluorescence is desired but color strength is not 
required, then the preferred ratio of chromophore structural units to 
non-fluorescent structural units is 20:80 to 1:999, more preferably 10:90 
to 1:999 and more preferably 5:95 to 1:999. 
The weight ratio of structural elements of formula V to fluorescent 
structural units is dependent on the actual practical application, hence 
there are no well defined preferred ratios, other than the broad range 
0:100 to 999:1. In certain applications where both color strength and 
fluorescence are required, then the preferred ratios structural elements 
of formula V to fluorescent structural units is 20:80 to 1:999, more 
preferably 10:90 to 1:999 and more preferably 5:95 to 1:999. In 
circumstances where fluorescence is desired but color strength is not 
required, then the preferred ratio structural elements of formula V to 
fluorescent structural units is 20:80 to 100:0, preferably 50:50 to 100:0 
and more preferably 80:20 to 100:0. 
The polymers with the structural elements of formulae IV and optionally V 
may be crosslinked with multi-functional monomers, for example with 0.01 
to 80 wt %, preferably 0.1 to 60 wt % of these monomers, related to the 
total weight of polymer. Depending upon the kind of polymer, it may be 
possible to use at least trifunctional carboxylic acids, isocyanates, 
alcohols, amines, vinyls or epoxides. It is also possible to employ 
polymerisates that contain at least two olefinically (ethylenically) 
unsaturated groups containing organic compounds. A wider range of 
crosslinking agents are well known to those familiar in the art. The 
ethylenically unsaturated crosslinking agents may be selected from the 
group consisting of divinylbenzol, bi-dimethylmaleinimid-alkylene 
bi-(dimethylmaleinimidyle)-methylene or -ethylene, acrylic acid- or 
methacrylic acid esters or -amides of polyols, preferably diols to 
tetrols, or polyamines respectively, preferably diamines to tetramines. 
Preferred crosslinking agents are selected from the group of aliphatic, 
cycloaliphatic and cycloaliphatic-aliphatic diols and diamines 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.6 alkylendiols 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 
polyethylenepolypropylenediols, further 1,1,1-trihydroxymethylethane or 
-propane, pentaerythrite and dipentaerythrite. 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, aminomethylcyclohexaneamine, 
isophorondiamine and di(aminomethyl)cyclohexane. 
In a preferred embodiment of the invention the polymers contain structural 
elements of the formula VI, 
##STR7## 
wherein R.sub.12 is H or methyl, and X.sub.1, X.sub.2, R.sub.1, R.sub.3, 
chromophore, r and s have the meanings given before, inclusive of the 
preferred embodiments; and optionally structural elements of formula V. 
The group -X.sub.1 -(R.sub.1).sub.r -(X.sub.2).sub.s -R.sub.3 - in the 
structural elements of formulae VI and VIa mean preferably -C(O)-O-, 
-C(O)-O-C.sub.1 -C.sub.6 alkylene-O- C(O)-, -C(O)-O-(C.sub.2 -C.sub.6 
alkylene-O).sub.u - C(O)- with u being a number of 2 to 10, phenylene or 
benzylene, -C(O)-C.sub.6 H.sub.5 -CH.sub.2 - or -C(O)-C.sub.1 to C.sub.12 
alkylene. 
The polymers with the structural elements of formulae IV or VI, and 
optionally structural elements of formula V may contain additionally equal 
or different structural elements of formula VII, 
##STR8## 
wherein R.sub.12, X.sub.1, X.sub.2, R.sub.1, R.sub.3, r and s have the 
meanings given before, inclusive of the preferred embodiments. These 
structural elements are preferably present when the chromophore group is 
introduced to the polymer through reaction between pendant functional 
groups on the polymer and functional groups on the respective chromophore 
molecules. 
The polymers with the structural elements of formulae IV or VI, and 
optionally structural elements of formula V, contain preferably equal or 
different structural elements of formula VIII as preferred units of 
formula V, 
##STR9## 
wherein 
R.sub.12 means H or methyl, and 
R.sub.13 means H, C.sub.1 -C.sub.4 alkyl, C.sub.1 -C.sub.4 alkoxy, -CN, Cl, 
phenyl, pyrrolidonyl, pyridinyl, imidazolyl, -C(O)OR.sub.14 or 
-C(O)-NR.sub.15 R.sub.16, 
R.sub.39 means H or C.sub.1 -C.sub.18 - and preferably C.sub.1 -C.sub.12 
alkyl, and 
R.sub.15 and R.sub.16 independently of one another mean H or C.sub.1 
-C.sub.12 -, and preferably C.sub.1 -C.sub.6 alkyl. 
The polymers with the structural elements of formulae IV and IVa, or VI and 
VIa, and optionally equal or different structural elements of formula V or 
formula VIII, may of agents additionally contain structural elements of 
formulae IX or X as preferred crosslinking, 
##STR10## 
wherein 
R.sub.12 means H or methyl, 
X.sub.3 means -O-, -NH- or -N(C.sub.1 -C.sub.4 -alkyl)-, and 
R.sub.17 means C.sub.2 -C.sub.12 - and preferably C.sub.1 -C.sub.6 
alkylene, cyclohexylene, cyclohexanedimethylene, phenylene, or X.sub.3 
means -O- and R.sub.17 means C.sub.2 -C.sub.6 alkylene-(C.sub.2 -C.sub.6 
alkylen-O).sub.2 to 20 - C.sub.2 -C.sub.6 alkylene. 
The polymerisates and preferred polymerisates described before may contain 
additionally equal or different ionic structural elements, for example of 
formula XI, 
##STR11## 
wherein 
R.sub.12 means H or methyl, 
R.sub.18 means H and R.sub.19 means -C(O)OR.sub.20, -SO.sub.3 R.sub.20, 
-C.sub.6 H.sub.4 -COOR.sub.20, -C.sub.6 H.sub.4 -SO.sub.3 R.sub.20, 
-C.sub.6 H.sub.4 -R.sub.21 or -C(O)-X.sub.4 -C.sub.2 -C.sub.6 
alkylene-R.sub.22, 
X4 means -O- or -NH-, 
R.sub.18 and R.sub.19 mean independently of one another -C(O)OR.sub.20 or 
-C(O)-X.sub.4 -C.sub.2 -C.sub.6 alkylene-R.sub.22, 
R.sub.20 means an alkaline metal, preferably Li, Na or K, 
R.sub.21 means an ammonium group or an ammoniummethyl group, and 
R.sub.22 means an ammonium group. 
The ammonium group or the ammonium in the ammoniummethyl group may be 
derived from primary, secondary or tertiary amine groups; preferred are 
quaternary ammonium groups. The ammonium groups or the ammonium in the 
ammoniummethyl group may correspond to the formula XII, 
EQU -.sup.+ NR.sub.23 R.sub.24 R.sub.25 (XII), 
wherein 
R.sub.23, R.sub.24 and R.sub.25 are independently from one another H, 
C.sub.1 -C.sub.18 -, preferably C.sub.1 -C.sub.12 - and more preferably 
C.sub.1 -C.sub.6 alkyl, C.sub.5 - or C.sub.6 cycloalkyl, phenyl, benzyl, 
1-phenyl-eth-2-yl, or 
R.sub.23 and R.sub.24 together are tetramethylene, pentamethylene or 
-CH.sub.2 CH.sub.2 -O-CH.sub.2 CH.sub.2 - and R.sub.26 has the meaning 
given before. 
Suitable counter anions may be derived from inorganic or organic acids, for 
example carboxylic acids, sulfonic acids and halogenhydrogen acids. 
Preferred counter anions are chloride and bromide. 
The polymerisates and preferred polymerisates described before may contain 
additionally structural elements with acidic groups like for example 
-C(O)OH or -SO.sub.3 H, especially when emulsion polymerisates are 
involved. 
The structural elements with acidic groups may correspond to the formula 
XIII, 
##STR12## 
wherein 
R.sub.12 means H or methyl, 
R.sub.27 means H and R.sub.26 means -C(O)OH, -SO.sub.3 H, -C.sub.6 H.sub.4 
-COOH, -C.sub.6 H.sub.4 -SO.sub.3 H, or 
R.sub.26 and R.sub.27 means -C(O)OH. 
Polymers with amino or acidic groups may be preferably soluble in water or 
they may be prepared by emulsion polymerization for dispersing and/or 
dissolving monomers. 
In another preferred embodiment the polymers according to the invention may 
be crosslinked with difunctional molecules. These polymers may contain 
recurring structural elements of formula XIV alone or together with 
structural elements of formula IV, 
##STR13## 
wherein 
R.sub.1, R.sub.3, R.sub.12, X.sub.1, X.sub.2, r, s, chromophore have the 
meanings given before, inclusive preferred embodiments. 
The weight ratio of structural elements of formula (XIV) to non-fluorescent 
structural units is dependent on the actual practical application, hence 
there are no well defined preferred ratios, other than the broad range 
100:0 to 1:999. In certain applications where both color strength and 
fluorescence are required, then the preferred ratios of chromophore 
structural units to non-fluorescent structural units is 20:80 to 100:0, 
preferably 50:50 to 100:0 and more preferably 80:20 to 100:0. In 
circumstances where fluorescence is desired but color strength is not 
required, then the preferred ratio of chromophore structural units to 
non-fluorescent structural units is 20:80 to 1:999, more preferably 10:90 
to 1:999 and more preferably 5:95 to 1:999. 
The above crosslinked polymers with one or both structural elements of 
formulae XIV may contain structural elements of formulae IV, V, VIII, IX, 
X, XI, XII and XIII alone or in any combination of at least 2 of these 
structural elements, or may contain structural elements of preferred 
residues formulae V, IX and VIII, and further IX, X, XI, XII and XIII 
alone or in any combination of at least 2 of these structural elements. 
Preferred divalent residues of the chromophore correspond to the formula 
XV, 
##STR14## 
wherein 
neighboring carbon atoms of the benzene rings can be condensed with benzene 
rings, heteroaromatic rings or both, and to these rings can be linked free 
bonds instead of the benzene rings of a polycyclic structure, and the 
aromatic rings are unsubstituted or substituted with halogen like F, Cl or 
Br, -CN, -NO.sub.2, C.sub.1 to C.sub.18 alkyl, 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.18 aryl-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.5 to C.sub.17 heteroaralkyl-SO- or -SO.sub.2, tertiary 
amino with 3 to 30 carbon atoms, and alkoxalkyl with 2 to 20 carbon atoms. 
The cyclic aliphatic and aromatic residues may be also be substituted, for 
example with halogens like F, Cl or Br; or -CN, -NO.sub.2, C.sub.1 to 
C.sub.18 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.6 to C.sub.18 aryl, 
, 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, and A.sub.6 and 
A.sub.7 mean a direct bond divalent organic group. 
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. 
Preferably 1 or 2 rings are condensed with the neighboring carbon atoms to 
form bicyclic or tricyclic systems. They may be selected from benzene, 
furane, thiophene, pyrrole, pyridine, and pyrimidine. 
In a preferred embodiment, A.sub.6 and A.sub.7 correspond to the formula 
XVI, 
EQU -X.sub.1 -(R.sub.1).sub.r -(X.sub.2).sub.s -R.sub.3 - (XVI), 
wherein 
X.sub.1, X.sub.2, R.sub.1, R.sub.3, r and s have the meanings as described 
before, inclusive of the preferred embodiments. 
In a preferred embodiment the bivalent chromophore residues correspond to 
formulae XVII and XVIIa, 
##STR15## 
wherein 
R.sub.01, R.sub.02, R.sub.03, R.sub.04, and R.sub.05 independently from one 
another mean H, Cl, C.sub.1 to C.sub.18 alkyl, C.sub.1 to C.sub.18 alkoxy, 
phenyl, benzyl, C.sub.1 to C.sub.12 alkylphenyl or C.sub.1 to C.sub.12 
alkylbenzyl. R.sub.05 means preferably H, and A.sub.6 and A.sub.7 
correspond to a bivalent residue of formula XVI. 
In a preferred embodiment the groups A.sub.6 and A.sub.7 may be selected 
from the formulae 
EQU -C(O)-O-R'-O-C(O)-(R").sub.u - and 
EQU -C(O)-NH-R'-NH-C(O)-(R").sub.u -, 
wherein R' is C.sub.2 to C.sub.20, preferably C.sub.2 to C.sub.12, and more 
preferably C.sub.2 to C.sub.6 alkylene, phenylene, benzylene, or 
oligoxyalkylene with preferably 2 to 6, and more preferably 2 to 4 
oxyethylene and/or oxypropylene units, R" means C.sub.1 to C.sub.12 
alkylene, phenylene or benzylene, and u means 0 or 1. 
Some preferred examples of chromophore residues corresponding to formula XV 
are 
##STR16## 
In another preferred embodiment of the invention the polymer according to 
the invention may contain or may be composed of functional chromophore 
monomers which contain two or three functional groups covalently linked 
via a bridging group to one ring of the chromophore core structure. Thus 
the polymers with recurring structural units of the formulae III, IIIa and 
IIIb may additionally contain, or the units of the formula IIIb may be 
replaced by recurring crosslinking units of the formula IIIc, IIId or 
both, 
##STR17## 
wherein 
A.sub.8 means a trivalent or tetravalent organic residue, copolymerisable 
with the groups A to A.sub.2, and 
Chromophore means a monovalent fluorescent chromophore, as defined before. 
Preferred divalent and trivalent residues of the chromophore may also 
correspond to the formulae XX and XXa, 
##STR18## 
wherein 
neighboring carbon atoms of the benzene ring can be condensed with benzene 
rings, heteroaromatic rings or both, and the aromatic rings are 
unsubstituted or substituted with halogens like F, Cl or Br, -CN, 
-NO.sub.2, C.sub.1 to C.sub.18 alkyl, 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.18 aryl-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.5 to C.sub.17 heteroaralkyl-SO- or -SO.sub.2, tertiary 
amino with 3 to 30 carbon atoms, and alkoxyalkyl with 2 to 20 carbon 
atoms, the cyclic aliphatic and aromatic residues (substituents) may also 
be substituted, for example with halogens like F, Cl or Br; or -CN, 
-NO.sub.2, C.sub.1 to C.sub.18 alkyl, C.sub.3 to C.sub.12 cycloalkyl, 
C.sub.6 to C.sub.18 aryl, 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, 
and A.sub.8 mean a trivalent or tetravalent organic group. 
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. 
Preferably 1 ring is condensed with the neighboring carbon atoms to form 
bicyclic systems. They may be selected from benzene, furane, thiophene, 
pyrrole, pyridine, and pyrimidine. 
In a preferred embodiment, A.sub.8 corresponds to the formulae XXI or XXIa, 
##STR19## 
wherein 
(a) R.sub.31 is a direct bond, C.sub.1 to C.sub.12 alkylene, phenylene or 
benzylene; 
X.sub.4 is N, O, S, C(O)O or C(O)N; 
R.sub.32 means C.sub.2 to C.sub.12 alkyltriyl, phenyltriyl or benztriyl, 
when a is 1 and b is 2, or means C.sub.2 to C.sub.12 alkyltetrayl, 
phenyltetrayl or benztetrayl, when a is 1 and b is 3; 
X.sub.5 means O, S, NH, C(O)O, C(O)NH, 
##STR20## 
(b) R32 is a bond, a is 0 and b is 2 or 3, X.sub.5 has the above meanings 
and R.sub.31 means C.sub.2 to C.sub.12 alkyltriyl, phenyltriyl or 
benztriyl, when b is 2, or means C.sub.2 to C.sub.12 alkyltetrayl, 
phenyltetrayl or benztetrayl, when b is 3; 
(c) R.sub.31 is a direct bond, C.sub.1 to C.sub.12 alkylene, phenylene or 
benzylene; 
X.sub.6 is N or C(O)N; 
R.sub.33 is C.sub.2 to C.sub.12 alkylene; 
X.sub.7 is O, S, C(O)O, C(O)NH, and 
##STR21## 
R.sub.31 and R.sub.33 in the meaning of alkylene contain preferably 2 to 8 
and mostly preferred 2 to 4 C-atoms. R.sub.32 in the meaning of alktriyl 
contain preferably 2 to 8, more preferred 2 to 6, and mostly preferred 2 
to 4 C-atoms. 
In a preferred embodiment the bivalent chromophore residues correspond to 
formulae XXII and XXIIa, 
##STR22## 
wherein 
R.sub.01, R.sub.02, R.sub.03, R.sub.04, and R.sub.05 independently from one 
another mean H, Cl, C.sub.1 to C.sub.18 alkyl, C.sub.1 to C.sub.18 alkoxy, 
phenyl, benzyl, C.sub.1 to C.sub.12 alkylphenyl or C.sub.1 to C.sub.12 
alkylbenzyl, and A8 correspond to formulae XXI or XXIa. R.sub.05 means 
preferably H. 
In a preferred embodiment the group A.sub.8 may be selected from the group 
##STR23## 
Some preferred examples are residues from the group (Ph means phenyl): 
##STR24## 
The polymers according to the invention may be random, block, graft or 
emulsion polymers (latices). 
The preparation of polymers and their immobilization is well known in the 
art. In principle there may be used two procedures. In a first aspect it 
is possible to polymerize monomers with pendent chromophore molecules. In 
a second aspect it is possible to use polymers with pendent functional 
groups and to react them with chromophore molecules containing functional 
groups. 
A further preferred embodiment of the invention is a process for the 
manufacture of the polymers according to the invention, which comprises 
reacting a compound of the formula XVIII, XIX, and XXIII and in any 
combination, alone or together with comonomers, 
EQU A'.sub.1 --chromophore (XVIII) 
EQU A'.sub.2 --chromophore--A'.sub.2 (XIX) 
EQU Chromophore-(A'.sub.3).sub.c (XXIII) 
wherein 
A'.sub.1 is a monovalent functional or polymerisable group, 
A'.sub.2 is a monovalent functional or polymerisable group coreactive with 
A'.sub.1, 
A'.sub.3 is a monovalent functional or polymerisable group coreactive with 
functional or polymerisable groups on the polymer and c is 2 or 3, and 
Chromophore has the meaning given before, whereby the A'.sub.1, A'.sub.2 
and A'.sub.3 are linked directly or via a bridging group to the 
chromophore body. 
A further preferred embodiment of the present invenion relates to a process 
for the manufacture of the inventive composition, which comprises reacting 
a polymer with recurring structural elements containing, either directly 
or through a bridging group, covalently linked functional or polymerisable 
groups, with a compound of the formula XVIII, XIX and/or XXIII in any 
chromophore combination, alone or together with comonomers, 
EQU A'.sub.1 --Chromophore (XVIII) 
EQU A'.sub.2 --chromophore--A'.sub.2 (XIX) 
EQU Chromophore-(A'.sub.3).sub.c (XXIII) 
wherein 
A'.sub.1 is a monovalent functional or polymerisable group, 
A'.sub.2 is a monovalent functional or polymerisable group coreactive with 
functional or polymerisable groups of the polymer, 
A'.sub.3 is a monovalent functional or polymerisable group coreactive with 
functional or polymerisable groups on the polymer and c is 2 or 3, and 
Chromophore has the meaning as given before, whereby the A'.sub.1, A'.sub.2 
and A'.sub.3 are linked directly, or via a bridging group, to the 
chromophore body. 
The preparation of the polymers according to the invention may be carried 
out according to processes well known in the art of polymer chemistry for 
example step-growth, anionic, cationic and radical polymerisations. Known 
polymerization processes are solution, bulk, emulsion, photo- and 
interface polymerization. 
Reaction temperatures may range from 0 to 250.degree. C. The use of 
suitable catalysts and photoinitiators as known and not described here. 
However, azobisisobutyronitrile is a well known and effective radical 
catalyst for the thermal polymerisations of olefinically unsaturated 
compounds. The polymerization may be carried out by mixing the monomers, 
catalysts, and optionally a solvent, together and heating, irradiating or 
by both heating and irradiating. The polymers may be isolated by 
precipitation with non-solvents or removing solvents and optionally 
purified by repeat precipitations and drying. 
The monomers are partially novel and partially known or they can be 
prepared by known or analogous methods. 
Difunctional benzo[4,5]imidazo[2,1-a]isoindol-11-ones are novel, and in one 
aspect, and a further preferred embodiment of the invention, are compounds 
of formula XXIV, 
EQU A".sub.1 --Chromophore--A".sub.1 (XXIV), 
wherein 
A".sub.1 is a monovalent functional (also means polymerisable) group, which 
is linked directly or via a bridging group to the chromophore body, and 
Chromophore is a divalent benzo[4,5]imidazo[2,1-a]isoindol-11-one, 
neighboring carbon atoms of the benzene rings of the chromophore can be 
condensed with benzene rings, heteroaromatic rings or both, and to these 
rings can be linked the free bond rather than to the benzene rings of the 
chromophore core structure, and the aromatic rings are unsubstituted or 
substituted with F, Cl or Br, -CN, -NO.sub.2, C.sub.1 to C.sub.18 alkyl, 
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.18 
aryl-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.5 to C.sub.17 heteroaralkyl-SO- or 
-SO.sub.2, tertiary amino with 3 to 30 carbon atoms, and alkoxyalkyl with 
2 to 20 carbon atoms, with the proviso that two -NH.sub.2 groups are not 
bond directly to different benzene rings and two OH groups are not 
directly bond to one ring of the benzo[4,5]imidazo[2,1-a]isoindol-11-one 
core structure. 
The cyclic aliphatic and aromatic residues may be also substituted, with 
for example F, Cl or Br, -CN, -NO.sub.2, C.sub.1 to C.sub.18 alkyl, 
C.sub.3 to C.sub.12 cycloalkyl, C.sub.6 to C.sub.18 aryl, , 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. 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. 
Preferably 1 or 2 rings are condensed with the neighboring carbon atoms to 
form bicyclic or tricyclic systems. They may be selected from the group 
consisting of benzene, furane, thiophene, pyrrole, pyridine, and 
pyrimidine. 
In a preferred embodiment, the bridging group corresponds to the formula 
XXV, 
EQU -X.sub.1 -(R.sub.1).sub.r -(X.sub.2).sub.s -R.sub.3 - (XXV), 
wherein 
X.sub.1, X.sub.2, R.sub.1, R.sub.3, r and s have the meanings given before, 
inclusive of the preferred embodiments. 
The functional groups A'.sub.1 may be selected from the group consisting of 
alkyl bonded halogen like Cl and Br; -N.sub.3, epoxide, -OH, -SH, -CN, 
-NHR.sub.100, .dbd.C.dbd.NR.sub.100, .dbd.CO, -CH-O, -NCO, 
-CH.dbd.CH.sub.2, -C(CH.sub.3).dbd.CH.sub.2, -C(O)OH, -SO.sub.3 H, 
-SO.sub.2 Cl, -SO.sub.2 Br, -C(O)-Cl, -C(O)-Br, -OC(O)-OR.sub.101, 
-OC(O)-NR.sub.102 R.sub.103, -C(O)-OR.sub.104, -SO.sub.2 -OR.sub.104, 
-C(O)-NR.sub.102 R.sub.103, and -SO.sub.2 - NR.sub.102 R.sub.103, wherein 
R.sub.100 means H, C.sub.1 -C.sub.18 alkyl, phenyl, or benzyl, 
R.sub.101 means C.sub.1 -C.sub.18 alkyl, phenyl, or benzyl, 
R.sub.102 and R.sub.103 independently from one another means H, C.sub.1 
-C.sub.18 alkyl, phenyl, or benzyl, and 
R.sub.104 means C.sub.1 -C.sub.18 alkyl, phenyl, or benzyl. 
R.sub.100, R.sub.101, R.sub.102, R.sub.103 and R.sub.104 contain as alkyl 
preferably 1 to 12, more preferably 1 to 8 and most preferably 1 to 4 
carbon atoms. 
More preferred functional groups A'.sub.1 are selected from the group 
consisting of alkyl linked Cl and Br; epoxide, -OH, -SH, -NHR.sub.100, 
-CH.dbd.CH.sub.2, -C(CH.sub.3).dbd.CH.sub.2, -NCO, -C(O)OH, -C(O)-Cl, 
-C(O)-Br, -C(O)-OR.sub.104, -C(O)- NR.sub.102 R.sub.103, wherein 
R.sub.100 means H or C.sub.1 -C.sub.12 alkyl, 
R.sub.102 and R.sub.103 independently from one another means H or C.sub.1 
-C.sub.4 alkyl, and 
R.sub.104 means C.sub.1 -C.sub.8 alkyl. 
In a mostly preferred embodiment the compounds correspond to formulae XXVI 
and XXVIa, 
##STR25## 
wherein 
R.sub.01, R.sub.02, R.sub.03, R.sub.04, and R.sub.05 independently from one 
another mean H, Cl, C.sub.1 to C.sub.18 alkyl, C.sub.1 to C.sub.18 alkoxy, 
phenyl, benzyl, C.sub.1 to C.sub.12 alkylphenyl or C.sub.1 to C.sub.12 
alkylbenzyl, A.sub.6 and A.sub.7 correspond to a bivalent residue of 
formula XXXIII, and A".sub.3 is selected from the group consisting of 
alkyl linked Cl and Br; epoxide, -OH, -SH, -NHR.sub.100, -CH.dbd.CH.sub.2, 
-C(CH.sub.3).dbd.CH.sub.2, -NCO, -C(O)OH, -C(O)-Cl, -C(O)-Br, 
-C(O)-OR.sub.104, -C(O)- NR.sub.102 R.sub.103, wherein 
R.sub.100 means H or C.sub.1 -C.sub.12 alkyl, 
R.sub.102 and R.sub.103 independently from one another means H or C.sub.1 
-C.sub.4 alkyl, and 
R.sub.104 means C.sub.1 -C.sub.8 alkyl, R.sub.05 means preferably H. 
In an especially preferred embodiment the bivalent groups A.sub.6 and 
A.sub.7 may be selected from the formulae 
EQU -C(O)-O-R'-O-C(O)-(R").sub.u - and 
EQU -C(O)-NH-R'-NH-C(O)-(R").sub.u -, 
wherein R' is C.sub.2 to C.sub.20, preferably C.sub.2 to C.sub.12, and more 
preferably C.sub.2 to C.sub.6 alkylene, phenylene, benzylene, or 
oligoxyalkylene with preferably 2 to 6, and more preferably 2 to 4 
oxyethylene and/or oxypropylene units, R" means C.sub.1 to C.sub.12 
alkylene, phenylene or benzylene, and u means 0 or 1, and groups 
-CH.dbd.CH.sub.2 or -C(CH.sub.3).dbd.CH.sub.2 are linked to the 
C(O)-groups. 
Especially preferred compounds correspond to the formula XXVII, 
##STR26## 
wherein 
A.sub.6 is C.sub.6 H.sub.4 and A.sub.7 is a direct bond or C.sub.1 to 
C.sub.6 alkylene, phenylene or benzylene, and A".sub.3 means -COOH, 
-C(O)-Cl, -C(O)-Br, -C(O)-OR.sub.104, -C(O)- NR.sub.102 R.sub.103, 
-C(O)O-C.sub.2 to C.sub.12 alkylene-OH, -C(O)O-C.sub.2 to C.sub.12 
alkylene-O-C(O)-CH.dbd.CH.sub.2, or -C(O)O-C.sub.2 to C.sub.12 
alkylene-O-C(O)-C(CH.sub.3).dbd.CH.sub.2. 
Monofunctional benzo[4,5]imidazo[2,1-a]isoindol-11-ones except amino, 
hydroxyl and carboxylphenyl substituted derivatives, and 
benzo[4,5]imidazo[2,1-a]isoindol-11-ones with one polyfunctional 
substituent are also novel, furthermore, in one aspect, and a further 
preferred embodiment of the invention, are compounds of formulae XXVIII 
and XXVIIIa, 
EQU Chromophore-A".sub.4 (XXVIII), 
EQU Chromophore-A".sub.5 (XXVIIIa), 
wherein 
A".sub.4 is a monovalent functional (also means polyrmerisable) group, 
which is linked directly or via a bridging group to the chromophore core 
structure, 
A".sub.5 is a di- or trifunctional (also means polymerisable) group, which 
is linked directly or via a bridging group to the chromophore core 
structure, and 
Chromophore is a monovalent benzo[4,5]imidazo[2,1 -a]isoindol- 11-one, 
neighboring carbon atoms of the benzene rings of the chromophore can be 
condensed with benzene rings, heteroaromatic rings or both, and to these 
rings can be linked the free bond rather than to the benzene rings of the 
chromophore core structure, and the aromatic rings are unsubstituted or 
substituted with F, Cl or Br, -CN, -NO.sub.2, C.sub.1 to C.sub.18 alkyl, 
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.1 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.1 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.18 
aryl-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.5 to C.sub.17 heteroaralkyl-SO- or 
-SO.sub.2, tertiary amino with 3 to 30 carbon atoms, and alkoxyalkyl with 
2 to 20 carbon atoms, with the proviso, that in compounds of formula 
XXVIII, the group OH is linked via a bridging group, that the group 
-NH.sub.2 is not bonded directly or via phenylene bridging group, and that 
the group COOH is not bonded via a phenylene bridging group to the benzene 
rings of the benzo[4,5]imidazo[2,1-a]isoindol-11-one core structure. 
The cyclic aliphatic and aromatic residues (substituents) may be also 
substituted, with for example F, Cl or Br, -CN, -NO.sub.2, C.sub.1 to 
C.sub.18 alkyl, C.sub.3 to C.sub.12 cycloalkyl, C.sub.6 to C.sub.18 aryl, 
, 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. 
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. 
Preferably 1 or 2 rings are condensed with the neighboring carbon atoms to 
form bicyclic or tricyclic systems. They may be selected from the group 
consisting of benzene, furane, thiophene, pyrrole, pyridine, and 
pyrimidine. 
In a preferred embodiment, the bridging group in compounds of formula 
XXVIII corresponds to the formula XXIX, 
EQU -X.sub.1 -(R.sub.1).sub.r -(X.sub.2).sub.s -R.sub.3 - (XXIX), 
wherein 
X.sub.1, X.sub.2, R.sub.1, R.sub.3, r and s have the meanings given before, 
inclusive of the preferred embodiments. 
The functional groups A".sub.4 and A".sub.5 may be selected from the group 
consisting of halogens like Cl and Br; -N.sub.3, epoxide, -OH, -SH, -CN, 
-NHR.sub.100, .dbd.C.dbd.NR.sub.100, .dbd.CO, -CH.dbd.O, -NCO, 
-CH.dbd.CH.sub.2, -C(CH.sub.3).dbd.CH.sub.2, -C(O)OH, -SO.sub.3 H, 
-SO.sub.2 Cl, -SO.sub.2 Br, -C(O)-Cl, -C(O)-Br, -OC(O)-OR.sub.101, 
-OC(O)-NR.sub.102 R.sub.103, -C(O)-OR.sub.104, -SO.sub.2 -OR.sub.104, 
-C(O)- NR.sub.102 R.sub.103, and -SO.sub.2 - NR.sub.102 R.sub.103, 
wherein 
R.sub.100 means H, C.sub.1 -C.sub.18 alkyl, phenyl, or benzyl, 
R.sub.101 means C.sub.1 -C.sub.18 alkyl, phenyl, or benzyl, 
R.sub.102 and R.sub.103 independently from one another means H, C.sub.1 
-C.sub.18 alkyl, phenyl, or benzyl, and 
R.sub.104 means C.sub.1 -C.sub.18 alkyl, phenyl, or benzyl. 
R.sub.100, R.sub.101, R.sub.102, R.sub.103 and R.sub.104 contain as alkyl 
preferably 1 to 12, more preferably 1 to 8 and most preferably 1 to 4 
carbon atoms. 
More preferred functional groups A".sub.4 and A".sub.5 are selected from 
the group consisting of alkyl linked Cl and Br; epoxide, -OH, -SH, 
-NHR.sub.100, -CH.dbd.CH.sub.2, -C(CH.sub.3).dbd.CH.sub.2, -NCO, -C(O)OH, 
-C(O)-Cl, -C(O)-Br, -C(O)-OR.sub.104, -C(O)- NR.sub.102 R.sub.103, 
wherein 
R.sub.100 means H or C.sub.1 -C.sub.12 alkyl, 
R.sub.102 and R.sub.103 independently from one another means H or C.sub.1 
-C.sub.4 alkyl, and 
R.sub.104 means C.sub.1 -C.sub.8 alkyl. 
In a mostly preferred embodiment the compounds of formula XXVIII correspond 
to formulae XXX and XXXa, 
##STR27## 
wherein 
R.sub.01, R.sub.02, R.sub.03, R.sub.04, and R.sub.05 independently from one 
another mean H, Cl, C.sub.1 to C.sub.18 alkyl, C.sub.1 to C.sub.18 alkoxy, 
phenyl, benzyl, C.sub.1 to C.sub.12 alkylphenyl or C.sub.1 to C.sub.12 
alkylbenzyl, A.sub.9 is a direct bond or correspond to a bivalent residue 
of formula XXXIII, and A".sub.4 is selected from the group consisting of 
alkyl linked Cl and Br; epoxide, -OH, -SH, -NHR.sub.100, -CH.dbd.CH.sub.2, 
-C(CH.sub.3).dbd.CH.sub.2, -NCO, -C(O)OH, -C(O)-Cl, -C(O)-Br, 
-C(O)-OR.sub.104, -C(O)-NR.sub.102 R.sub.103, 
wherein 
R.sub.100 means H or C.sub.1 -C.sub.12 alkyl, 
R.sub.102 and R.sub.103 independently from one another means H or C.sub.1 
-C.sub.4 alkyl, and 
R.sub.104 means C.sub.1 -C.sub.8 alkyl. R.sub.05 means preferably H. 
In an especially preferred embodiment the bivalent group A.sub.9 is a 
direct bond, C.sub.1 to C.sub.12 alkylene, phenylene, benzylene, C.sub.1 
to C.sub.12 oxyalkylene, oxyphenylene, oxybenzylene, C.sub.1 to C.sub.12 
thioalkylene, thiophenylene, thiobenzylene, or the bivalent group may be 
selected from the formulae 
EQU -C(O)-O-R'-O-C(O)-(R").sub.u - and 
EQU -C(O)-NH-R'-NH-C(O)-(R").sub.u -, 
wherein R' is C.sub.2 to C.sub.20, preferably C.sub.2 to C.sub.12, and more 
preferably C.sub.2 to C.sub.6 alkylene, phenylene, benzylene, or 
oligoxyalkylene with preferably 2 to 6, and more preferably 2 to 4 
oxyethylene and/or oxypropylene units, R" means C.sub.1 to C.sub.12 
alkylene, phenylene or benzylene, and u means 0 or 1, and groups 
-CH.dbd.CH.sub.2 or -C(CH.sub.3).dbd.CH.sub.2 are linked to the 
C(O)-groups. 
Especially preferred compounds correspond to the formula XXVIII are 
##STR28## 
wherein 
A.sub.9 is a direct bond or C.sub.1 to C.sub.6 alkylene, phenylene or 
benzylene, and A".sub.4 means -COOH, -C(O)-Cl, -C(O)-Br, -C(O)-OR.sub.104, 
-C(O)- NR.sub.102 R.sub.103, -C(O)O-C.sub.2 to C.sub.12 alkylene-OH, 
-C(O)O-C.sub.2 to C.sub.12 alkylene-O-C(O)-CH.dbd.CH.sub.2, or 
-C(O)O-C.sub.2 to C.sub.12 alkylene-O-C(O)-C(CH.sub.3).dbd.CH.sub.2. 
Examples of compounds of formula XXVIII are (Ph means phenyl): 
##STR29## 
wherein 
R.sub.34 is Cl, OH, OR.sub.104 and R.sub.104 means C.sub.1 -C.sub.8 alkyl, 
NR.sub.102 R.sub.103 and R.sub.102 and R.sub.103 independently from one 
another mean H, C.sub.1 -C.sub.4 alkyl or C.sub.2 to C.sub.4 hydroxyalkyl, 
-C(O)O-C.sub.2 to C.sub.12 alkylene-O-C(O)-CH.dbd.CH.sub.2, -C(O)O-C.sub.2 
to C.sub.12 alkylene-O-C(O)-C(CH.sub.3).dbd.CH.sub.2, -C(O)ONH-C.sub.2 to 
C.sub.12 alkylene-O-C(O)-CH.dbd.CH.sub.2, or -C(O)NH-C.sub.2 to C.sub.12 
alkylene-O-C(O)-C(CH.sub.3).dbd.CH.sub.2 ; 
##STR30## 
wherein R.sub.35 is a direct bond, methylene, ethylidene, 2,2-propylidene, 
O, S, NH, N(C.sub.1 to C.sub.4 alkyl), C(O) or C(O)NH, and R.sub.34 has 
the meaning given before; 
##STR31## 
wherein R.sub.35 has the meaning given before and R.sub.36 means H, 
C.sub.2 to C.sub.4 hydroxyalkyl, glycidyl or OR.sub.36 means NH-glycidyl 
or NHC.sub.2 to C.sub.4 hydroxyalkyl; and 
##STR32## 
Preferred compounds of formula XXVIII correspond to the formulae XXXII and 
XXXIIa, 
##STR33## 
wherein 
neighboring carbon atoms of the benzene ring can be condensed with benzene 
rings, heteroaromatic rings or both, and the aromatic rings are 
unsubstituted or substituted with halogens like F, Cl or Br, -CN, 
-NO.sub.2, C.sub.1 to C.sub.18 alkyl, 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.18 aryl-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.5 to C.sub.17 heteroaralkyl-SO- or -SO.sub.2, tertiary 
amino with 3 to 30 carbon atoms, and alkoxyalkyl with 2 to 20 carbon 
atoms, the cyclic aliphatic and aromatic residues (substituents) may also 
be substituted, for example with halogens like F, Cl or Br; or -CN, 
-NO.sub.2, C.sub.1 to C.sub.18 alkyl, C.sub.3 to C.sub.12 cycloalkyl, 
C.sub.6 to C.sub.18 aryl, , 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, and A.sub.10 means a trivalent and A.sub.11 means tetravalent 
organic group. 
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. 
Preferably the ring without the functional group is condensed with the 
neighboring carbon atoms to form bicyclic systems. They may be selected 
from benzene, furane, thiophene, pyrrole, pyridine, and pyrimidine. 
In a preferred embodiment, A.sub.10 corresponds to the formula XXXIII and 
A.sub.11 corresponds to formula XXXIIIa, 
##STR34## 
wherein 
(a) R.sub.31 is a direct bond, C.sub.1 to C.sub.12 alkylene, phenylene or 
benzylene; 
X.sub.4 is N, O, S, C(O)O or C(O)N; 
R.sub.32 means C.sub.2 to C.sub.12 alkyltriyl, phenyltriyl or benztriyl, 
when a is 1 and b is 2, or means C.sub.2 to C.sub.12 alkyltetrayl, 
phenyltetrayl or benztetrayl, when a is 1 and b is 3; 
X.sub.8 means OH, SH, NH.sub.2, C(O)OH, C(O)NH.sub.2, 
OC(O)-CH.dbd.CH.sub.2, OC(O)-C(CH.sub.3).dbd.CH.sub.2, 
HNC(O)-CH-.dbd.CH.sub.2, HNC(O)-C(CH.sub.3).dbd.CH.sub.2 ; or 
(b) R.sub.32 is a bond, a is 0 and b is 2 or 3, X.sub.8 has the above 
meanings and R.sub.31 means C.sub.2 to C.sub.12 alkyltriyl, phenyltriyl or 
benztriyl, when b is 2, or means C.sub.2 to C.sub.12 alkyltetrayl, 
phenyltetrayl or benztetrayl, when b is 3; 
(c) R.sub.31 is a direct bond, C.sub.1 to C.sub.12 alkylene, phenylene or 
benzylene; 
X.sub.9 is N or C(O)N; 
R.sub.33 is C.sub.2 to C.sub.12 alkylene; 
X.sub.10 is OH, SH, C(O)OH, C(O)NH.sub.2, or OC(O)-CH.dbd.CH.sub.2, 
OC(O)-C(CH.sub.3).dbd.CH.sub.2, HNC(O)-CH.dbd.CH.sub.2, 
HNC(O)-C(CH.sub.3).dbd.CH.sub.2 or -CH.dbd.CH.sub.2. 
R.sub.31 and R.sub.33 in the meaning of alkylene contain preferably 2 to 8 
and mostly preferred 2 to 4 C-atoms. R.sub.32 in the meaning of alktriyl 
contain preferably 2 to 8, more preferred 2 to 6, and mostly preferred 2 
to 4 C-atoms. 
In a preferred embodiment the polyfunctional compounds correspond to 
formulae XXXIV and XXXIVa, 
##STR35## 
wherein 
R.sub.01, R.sub.02, R.sub.03, R.sub.04, and R.sub.05 independently from one 
another mean H, Cl, C.sub.1 to C.sub.18 alkyl, C.sub.1 to C.sub.18 alkoxy, 
phenyl, benzyl, C.sub.1 to C.sub.12 alkylphenyl or C.sub.1 to C.sub.12 
alkylbenzyl, A.sub.10 correspond to formula XXXIII and A.sub.11 
corresponds to formula XXXIIIa. R.sub.05 means preferably H. 
In a preferred embodiment the group A.sub.10 and A.sub.11 may be selected 
from the group 
##STR36## 
Some preferred examples of compounds of formulae XXXII and XXXIIa are 
compounds from the group (Ph means phenyl): 
##STR37## 
The chromophore monomers can be prepared according to the methods described 
in EP-A 0 456 609 wherein phthalic anhydrides are reacted with 
1,2-diaminobenzenes, whereby the anhydride, the diaminobenzenes, or both, 
contain optionally protected functional groups. 
As preferred examples for difunctional chromophores the following compounds 
may be mentioned: 
##STR38## 
which may be synthesized starting from the corresponded acid chloride, for 
example by carrying out the reaction in a solvent like dry pyridine and 
thereby adding a, preferably large, excess of hydroxy ethyl methacrylate, 
preferably dissolved in the same solvent. Workup may be done by pouring 
the completed reaction mixture slowly on ice which may contain an acid 
like HCl, yielding a precipitate, which may be filtered and dried, for 
example by vacuum pumping. This crude precipitate preferably may be 
further purified, to remove residual hydroxyethyl methacrylate, by 
re-precipitation for example from chloroform into a large excess of 
hexane. 
The corresponding acid chloride may be synthesized preferably reaction of 
the corresponding diacid compound with thionyl chloride, preferably in a 
solvent like dry benzene. The reaction mixture may be heated to complete 
the reaction, for example to reflux temperature. Solvent and excess 
thionyl chloride can be removed preferably using a stream of nitrogen. 
The corresponding diacid compound may be synthesized for example starting 
from biphenyl-3,4,3' tricarboxylic acid, which is obtainable in accordance 
with the method described in Zh. Org. Khim 2(7), 1288 (1966), by reaction 
with 3,4-diamino benzoic, preferably in a solvent like acetic anhydride. 
The obtained benzo[4,5]-imidazo[2,1-a]isoindol-11-one-carboxylic diacid 
may be filtered and washed as usual with for example water and methanol, 
and may be further purified by column chromatography using preferably 
chloroform as the eluting solvent. 
##STR39## 
which may be synthesized starting from the corresponding 
tetraphenyl-benzo[4,5]-imidazo[2,1 -a]isoindol-11-one-carboxylic acid 
chloride (obtainable in a similar manner as the abovementioned diacid 
chloride) by reaction with diallylamine, preferably dissolved in a solvent 
like dry pyridine. Workup may be carried out by pouring the reaction 
mixture in ice cold water, washing the obtained crude reaction product 
with water and dried it. Further purification may be done via column 
chromatography using for example chloroform as the eluting solvent. 
As an example for a preferable trifunctional chromophore the following 
compound may be manufactured: 
##STR40## 
The preparation of this compound may be carried out starting from the 
corresponding trifunctional OH-derivative of 
tetraphenyl-benzo[4,5]imidazo[2,1-a]isoindol-11-one with acryloylchloride, 
preferably in a solvent like dichloromethane. Workup may be carried out in 
pouring the reaction mixture in a large excess of water, followed by 
filtering the obtained precipitate. If desired the crude product may be 
washed further for example with water and methanol and then dried, for 
example in an atmosphere under reduced pressure. 
The corresponding trifunctional OH-derivative may be synthesized preferably 
by the reaction of pentaerythritol (large excess) with 
tetraphenyl-benzo[4,5]imidazo[2,1-a]isoindol-11-one-carboxylic acid 
chloride (obtainable by reaction of the corresponding carboxylic acid with 
thionyl chloride), preferably in a solvent like dry pyridine. Workup may 
be carried out as usual and described before. 
The process to prepare the materials and compounds according to the 
invention may employ an inert solvent. Inert means, that the choice of a 
solvent is determined by the reactivity of the respective ingredients, 
hence a solvent preferably is selected such that no undesired side 
reactions occur. Solvents may also be employed in the actual application 
of the materials of the instant invention. 
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, ether (bibutylether, 
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, 
pivalolactone), 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, toluole, xylole) and nitriles 
(acetonitrile, propionitrile, bezenentrile, phenylacetonitrile). 
The compound 1,2,3,4-tetraphenyl-benzo[4,5]imidazo[2,1 -a]isoindol-11-one 
and its derivatives, which are a preferred group of fluorescent compounds 
of this invention, possess an absorption maximum at around 370 nm, which 
lies in the UV region. However, their excitation wavelengths stretch from 
around 350 nm, in the UV, to 450 nm, in the visible region of the 
electromagnetic spectrum. Consequently, materials employing this class of 
compound, can span a broad number of applications as they readily 
facilitate themselves to excitation by both UV and daylight radiation 
sources. Correspondingly these materials can 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 as well as in printing inks. 
It is also possible to produce fluorescent images (high relief structures) 
by the well known photoresist technology. 
The compositions according to the invention may be used in various forms 
depending upon the end-use purpose: 
The polymers of completion form (A) may be milled or can be produced in the 
form of particles. A further preferred embodiment of the invention is a 
polymer according to the completion form (A) in the form of particles, 
especially finely divided particles. 
The average diameter or particle size may correspond to that of the 
particles according to completion form (B). The polymers according to the 
invention may be admixed with other polymers. A further preferred 
embodiment of the invention is a composition containing (a) a polymer 
substrate and (b) in a, preferably uniform, distribution a polymer 
according to the completion form (A). 
The amount of component (b) may be for example from 0.1 to 99.9 percent by 
weight, preferably 1.0 to 50 with respect to the total composition. The 
amount used depends essentially from the amount of chromophore structural 
units on the polymer of completion form (A) and on compatibility with the 
polymer substrate. 
The polymers may be selected from thermoplastics, thermosettings and 
structurally crosslinked polymers. The admixture of thermoplastics with 
thermoplastics of completion form (A) are polymeric alloys. The polymers 
may be homopolymers, copolymers, blockpolymers, graft polymers or random 
polymers. 
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, 
vinylchloride, vinyldichloride, 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, polysufones, polyketones, 
polyphenylsulfides, and polyacetales; cellulose and its esters and ethers, 
and starch or derivatives of starch. 
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. 
The thermoplastic compositions can be obtained by known mixing methods such 
as 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 polymer of completion form (A) is preferably low molecular weight and 
dissolved in the polymerisable mixture. 
In a further aspect of the invention polymer particles of completion form 
(B) or completion form (A) or both together may be used as filler for 
thermoplastic, thermosetting and structurally crosslinked polymers. 
A further preferred embodiment of this invention is a composition 
comprising (a) a polymer substrate, and (b) particles of the completion 
form (B), polymer particles of a polymer according to the completion form 
(A) or both uniformly distributed therein. 
The amount of the particles may for example be 0.01 to 90 wt- %, preferably 
0.1 to 90 wt- %, and more preferably 1 to 50 wt- % of the total 
composition. 
The polymer substrate may include those as described above. This 
composition can be easily prepared by known mixing methods as described 
above, whereby the particles are dispersed prior to the polymerization of 
a precursor composition. 
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 (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. 
The compositions of the invention me be used in the form of shaped 
articles, including the surface modified compositions of completion form 
(B). 
A further preferred embodiment of the invention is therefore a shaped 
article from (a) the composition according to the polymers of completion 
form (A), or (b) a composition of (b1) a polymer substrate containing 
either (b2) polymers according to the completion form (A), or (b3) 
particles of the polymers of completion form (A), of completion form (B) 
or both, alone or together with a polymer of the completion form (A), 
uniformly distributed in the polymer substrate. 
In another aspect the polymers and particles of the completion form (A) or 
the particles of the completion form (B) may be used as coatings on 
carrier materials, using the above mentioned compositions. 
Another preferred embodiment of the invention is a composition comprising 
(a) a carrier material and (b) at least on one surface a coating of 
(1) a polymer of completion form (A), 
(2) a polymer substrate containing uniformly distributed particles of the 
completion form (A), completion form (B) or both, or 
(3) a polymer mixture comprising a substrate polymer and in uniform 
distribution a soluble polymer of completion form (A) and in admixture 
particles of the completion form (A), completion form (B) or both. 
Suitable carrier materials may be selected from 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. 
The thickness of the coating depends on the desired end-use and may be from 
0.1 to 1000 .mu.m, preferably 0.5 to 500 .mu.m, and especially preferred 1 
to 100 .mu.m. 
The coatings may be protected by covering coatings which are preferably 
transparent. Such coatings are well known, and in general photocrosslinked 
coatings are mainly used for this purpose. Moreover, the materials 
belonging to completion form (A), which are surface modified, may also be 
protected by coatings. 
The coated materials are obtainable by known methods like painting, casting 
or spincoating, directly or with a solution or dispersion of the polymeric 
compositions. It is also possible to use a polymerisable composition 
containing polymer forming monomers, especially crosslinkable olefinically 
unsaturated monomers. The polymerization may be induced thermally or by 
actinic radiation. The coating compositions are novel and a further 
preferred embodiment of the invention. 
A further preferred embodiment of the invention is therefore a liquid and a 
solvent containing composition, comprising; 
(1) a polymer of completion form (A), and optionally a nonfluorescent 
polymer, 
(2) a polymer substrate containing uniformly dispersed particles of the 
completion form (A), (B) or both, alone or in admixture with a soluble 
polymer of completion form (A). 
These compositions may contain a solvent, such as those mentioned before, 
and optionally surfactants and dispersing agents. The viscosity range 
depends on the final application for the coating wherein the desired 
viscosity can be achieved by choice and quantity of solvent, polymers as 
binders and fluorescent materials. To further achieve a desired viscosity, 
thickening agents may additionally be used. Again suitable solvents have 
been mentioned. 
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. If particles should aggregate 
they may be redistributed by stirring. 
In a highly advantageous embodiment of preparing coatings, polymerisable 
compositions can be used, wherein a t least one surface of a carrier 
material is coated and subsequently polymerized by heat or radiation. 
Photopolymerizable mixtures can also be used to generate fluorescent 
images by known photoresist technology. 
A further preferred embodiment of the invention is a polymerisable 
composition comprising 
a) polymerisable monomers or prepolymers in admixture With particles of 
completion forms (A), (B) or both, and optionally dissolved therein a 
polymer according to completion for m (A); 
b) polymerisable monomers or prepolymers and dissolved therein a polymer 
according to completion form (A); or 
c) a polymerisable chromophore structure, which contains at least one 
polymerisable group or at least two functional groups or a prepolymer of 
it, and optionally nonfluorescent monomers or prepolymers copolymerisable 
with both that of the fluorescent chromophore monomer. 
The composition may be used to generate the polymers of completion form (A) 
as described before. Preferably the composition contains a solvent. The 
afore described embodiments also apply to this composition, inclusive of 
preferred embodiments. 
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 and/or 
photo-polymerized. 
Photopolymerisable monomers and prepolymers are well known in the art and 
for example are described 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. 
The photopolymerisable composition is particularly suitable to generate 
coatings and images. 
A further preferred embodiment of the invention is a composition comprising 
(a) a carrier material and on at least one surface of the carrier is (b) a 
high relief image of a polymerized photoresist material, which contains 
(b1) particles of completion forms (A), (B) or both in uniform 
distribution, and optionally dissolved therein a polymer according to 
completion form (A); 
(b2) uniformly distributed therein a polymer according to completion form 
(B); or 
(b3) a polymer from a photopolymerisable chromophore containing at least 
one polymerisable group or at least two functional photoreactive groups or 
a prepolymer of it, and optionally non-fluorescent monomers or prepolymers 
copolymerisable by irradiation with that of the chromophore containing 
monomer. 
A further preferred embodiment of the invention is a process for the 
preparation of fluorescent high relief images on a carrier. This involves 
irradiating under a mask or by laser writing, the above coated 
photopolymerisable composition (which has been dried and removed of 
solvent) on the carrier, developing the irradiated composition and finally 
removing the non-irradiated parts. 
Removal of the non-irradiated parts is mostly carried out by treatment with 
solvent. 
All the materials described before are highly fluorescent materials and can 
broadly be used in optical and electroptical devices. 
A further preferred embodiment of the invention is a process for the 
creation of fluorescent radiation which requires exciting, electrically or 
by UV/visible radiation, or both, a fluorescent composition of the instant 
invention. 
Another preferred embodiment of the invention is the use of the 
compositions according to the invention as fluorescent materials. 
The compound 1,2,3,4-tetraphenyl-benzo[4,5]imidazo[2,1-a]isoindol-11-one 
and its derivatives, which are representative of the class of chromophore 
compounds used in this invention, in general possess an absorption maximum 
at around 370 nm, which lies in the UV region. However, their excitation 
wavelengths usually stretch from around 350 nm, in the UV, to 450 nm, in 
the visible region of the electromagnetic spectrum. Consequently, these 
polymeric materials can span a broad number of applications as they 
readily facilitate themselves to excitation by both UV and daylight 
radiation sources. Therefore, these materials could be rendered very 
useful as coloring agents in applications such as road markings and 
traffic signs, as they exhibit brilliant daylight fluorescence and can 
also be excited by the UV radiation of a motor vehicles halogen lamp, 
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 or materials for 
generating fluorescent images etc. 
The composition of the present invention emits solid state fluorescence 
with a high emission intensity according to observations hitherto.

The following examples demonstrate the invention. 
A) Preparation of Mono-vinyl Fluorescent Compound (A3) and its 
Intermediates (A1, A2). 
EXAMPLE A1 
1,2,3,4 tetraphenyl- benzo[4,5]imidazo[2,1 -a]isoindol-11-one-7-carboxylic 
acid (A1, inclusive the corresponding 8-isomer) 
Into a reaction vessel equipped with a condenser, light nitrogen purge and 
magnetic stirrer, 10 g (0.022 mol) of tetraphenylphthalic anhydride and 
3.35 g (0.022 mol) of 3,4 diaminobenzoic acid are added, along with 100 ml 
of acetic acid. The gray colored reaction mixture is heated to reflux 
temperature. After several hours the reaction begins to take-on a dark 
yellow color. The reaction mixture is then left for a further 72 hours at 
slightly below reflux temperature (105.degree. C.). 
The bright yellow precipitate is filtered and washed with water and 
methanol. The yellow product is then left to dry at the water pump vacuum 
before final drying in a vacuum oven overnight (60.degree. C.). The 
obtained yield is 81%. 
EXAMPLE A2 
1,2,3,4 tetraphenyl-benzo[4,5]imidazo[2,1-a]isoindol-11-ones-7(or 8) 
carboxylic acid chloride (A2, inclusive the corresponding 8-isomer) 
Into a reaction vessel equipped with a condenser, light nitrogen purge and 
magnetic stirrer, 5 g (0.0088 mol) of compound A1 and 30 ml of dry benzene 
are added. Keeping at room temperature, a molar excess of thionyl chloride 
is added to the reaction mixture, which is then allowed to stir for 30 
minutes. The reaction mixture, which is a yellow suspension, is then 
heated to reflux temperature for about 2 hours, to yield a clear golden 
colored solution. The solvent and excess thionyl chloride are removed 
using a stream of nitrogen, to furnish the yellow acid chloride 
derivative. The yield is 94%. 
EXAMPLE A3 
1,2,3,4 tetraphenyl-11H-benzo[4,5]imidazo[2,1 -a]isoindol-11-ones-7-carboxy 
ethyl methacrylate (B1, inclusive the corresponding 8-isomer) 
4 g of A-2, dissolved in 30 ml of dry pyridine are added slowly over the 
period of about 30 minutes, to a stirred solution containing 5 g (large 
excess) hydroxy ethyl methacrylate in 10 ml of dry pyridine at room 
temperature. The reaction mixture is left at room temperature to stir for 
a further 2 hours. 
The completed reaction mixture is then slowly added, with stirring, to a 
beaker containing 100 g of ice and 100 ml of 1 M HCl. A yellow precipitate 
is obtained and allowed to settle before filtration (sinter glass G3), by 
vacuum pumping, to yield the crude product. The crude precipitate is 
further purified, to remove residual hydroxyethyl methacrylate, by 
re-precipitation from chloroform into a large excess of hexane (Yield 
86%). 
B) Preparation of Linear Copolymer containing a Fluorescent Chromophore 
2.04 g of solid-state fluorescent monomer A3, 1.7 g of freshly distilled 
methyl methacrylate, 0.0172 g of recrystallized AIBN 
(.alpha.,.alpha.'-azo-bisisobutyronitrile) and 12 ml of are added to a 
clean reaction flask. The reaction feed mixture is degassed by bubbling 
dry nitrogen gas through the mixture for 30 min and placed in a 
temperature controlled water bath at 60.degree. C. for 8 hours. The 
viscous solution is slowly poured into a large excess of methanol or 
hexane, where upon the a yellow precipitate is afforded. The polymer is 
purified by a further two reprecipitation. (Yield 53%, Mw 
2.5.times.10.sup.5 gmol.sup.-1). 
C) Preparation of a Solid-State Fluorescent Crosslinked Composition 
0.2337 g of A3, 0.5295 g of ethylene glycol dimethacrylate (EGDM) and 
0.2396 g, hydroxy ethyl methacrylate (HEMA), 0.0078 g of 
azobisisobutyronitrile (AIBN) and 1.5 ml of chloroform is removed of 
oxygen by bubbling nitrogen through the feed mixture. Whist maintaining a 
nitrogen atmosphere the monomer solution is added to 15 ml of vigorously 
stirred water. The water is itself removed of oxygen by bubbling with 
nitrogen for a period of 30 minutes. After a period of about 2 hours a 
mass of solid, insoluble crosslinked particles is furnished. Theses 
particles are filtered and washed several times in chloroform or DMF 
solution to remove all unreacted monomers. The afforded particles display 
intense solid-state fluorescence. (Yield 86%). 
Application Examples 
Photoluminescence and excitation spectra of all fluorescent polymer samples 
are recorded using a Hitachi F-4500 Fluorescence Spectrophotometer in the 
standard reflectance mode, with the aid of a commercial solid sampler that 
possesses a transparent quartz window. All polymer samples are ground into 
fine powders, via a standard laboratory mortar and pestle, and uniformly 
packed into the sample holder. The monochromatic excitation wavelength is 
365 nm and the scan rate 240 nm/min. The measured emission wavelength for 
various polymeric systems are detailed in Table 1. 
TABLE 1 
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Chromo- Emission 
Intensity 
Example 
phore Comonomers Maximum 
(arb. units) 
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B A3 MMA 498 nm 1001 
(54 wt %) 
(46 wt %) 
C A3 EGDM HEMA 494 nm 1120 
(23 wt %) 
(53 wt %) 
(24 wt %) 
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