Fluorescent Dyes and Pigments

Fluorescent Dyes and Pigments
RAMI ISMAEL, Aralon GmbH, Heiligenroth, Germany

HANSRUDOLF SCHWANDER, Ciba-Geigy AG, Basel, Switzerland
PAUL HENDRIX, Radiant Color NV, Houthalen, Belgium
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
Introduction . . . . . . . . . . . . . . . . .
1
Naphthalimide Dyes. . . . . . . . . . . .
2
Coumarin Dyes . . . . . . . . . . . . . . .
3
Xanthene Dyes . . . . . . . . . . . . . . .
4
Thioxanthene and Benzoxanthene Dyes 7
Naphtholactam, Hydrazam Dyes and
Homologues . . . . . . . . . . . . . . . . .
8
Azlactone Dyes . . . . . . . . . . . . . . .
9
Methine Dyes . . . . . . . . . . . . . . . .
9
Oxazine and Thiazine Dyes . . . . . . 10
Miscellaneous Fluorescent Dyes . . . 10
UV Fluorescent Chromophores with No
or Low Body Color . . . . . . . . . . . 12
Special Uses . . . . . . . . . . . . . . . . 13
Daylight Fluorescent Pigments. . . . 15
1. Introduction
Fluorescent dyes differ from normal dyes in
their exceptional bright colors. This is the result
of a combination of the reflexion of part of the
incident light and emission of light by the dye.
The major part of the light energy concentrates
at selected wavelengths. Fluorescent dyes are
used mainly as solvent, disperse, or reactive
dyes (! Disperse Dyes, ! Reactive Dyes) in
the coloring of textile fibers and plastics, in the
production of inks and printing inks and, in
combination with appropriate pigments, in the
production of paints and lacquers. Fluorescent
dyes are also employed as laser dyes (! Laser
Dyes). Furthermore, daylight and UV light
fluorescent dyes, mainly acid, basic, and solvent dyes, may be dissolved in a resin matrix or
covalently bound to a resin or a polymer and
then pulverized to form fluorescent pigments,
suspensions, and emulsions (see Chap. 13 Daylight Fluorescent Pigments).
Fluorescence occurs when molecules that
have absorbed light and are in their lowest
excited state S1 return to their ground state
# 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a11_279.pub2
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13.1.4.
13.1.5.
13.1.6.
13.2.
13.3.
13.4.
Production . . . . . . . . . . . . . . . . .
Dyes for Daylight Fluorescent
Pigments. . . . . . . . . . . . . . . . . . .
Pigment Matrices . . . . . . . . . . . .
Formaldehyde-Free and SolventResistant Fluorescent Pigments. . .
Sunlight Sensors . . . . . . . . . . . . .
Fluorescent Modifications with
Covalently Bound Dyes . . . . . . . .
More-Not Resinated-Solid-State
Fluorescent Pigments. . . . . . . . . .
Quality Specifications of Fluorescent
Pigments. . . . . . . . . . . . . . . . . . .
Applications of Fluorescent Pigments
Toxicology . . . . . . . . . . . . . . . . .
15
15
16
17
17
17
18
18
20
21
S0 and emit light (for a detailed discussion of

fluorescence, see ! Dyes, General Survey).
Some of the absorbed light energy also activates nuclear vibrations and is released as heat.
Further energy is lost due to the conversion of
the lowest excited state S1 to a triplet state T1
(intersystem crossing) and is not available for
fluorescence. The quantum yield is a measure
of the fluorescence efficiency of a compound, i.
e., the proportion of the absorbed light energy
that is emitted as fluorescent light.
Fluorescent dyes absorb in the UVand visible
region or solely in the visible region of the spectrum and emit light in the visible region of the
spectrum at longer wavelengths than blue. Some
of the fluorescent dyes emit in the infrared region
and have found specific applications in laser
writing and plastic welding applications. The
fluorescent dyes treated in this article are distinguished from optical or fluorescent brighteners
(! Optical Brighteners), which absorb in the
invisible UV region and emit blue to blue-violet
light,andfromtheUVsecuritydyes,whichabsorb
in the invisible UV region and also emit at longer
wavelength than blue but without having a so
Figure 1. Reflectance spectra of colored surfaces

a) Daylight fluorescent orange (ARACO 103 orange, ARALON GmbH, Germany); b) Theoretical white; c) Conventional
orange (Pigment Orange 73); d) Theoretical black
called body color. They appear colorless,

unless they are exposedto a UV light.Reflectance
spectra of various colored surfaces are shown in
Figure 1. Furthermore, neither the abovementioned fluorescent infrared dyes are treated
in this article, nor anti-stokes fluorescent dyes.
Fluorescent dyes usually have rigid,
extended p systems. Rigidity is of importance
because it suppresses the release of energy due
to activated nuclear vibrations.
There are many examples explaining the

importance of rigidity for showing fluorescence, like the fluorescent boradiazaindacene
as compared with the nonfluorescent dipyrromethene (see above) or like the fluorescent
fluorescein as compared with the nonfluorescent phenolphthalein.
It is thought that the floppiness of a molecule allows more vibrational interactions which
increase internal conversion rates of quenching

fluorescent activity.
Substituents such as heavy atoms (bromine or
iodine) or nitro groups are detrimental to fluorescence because they favor intersystem crossing.
Many dyes exhibit fluorescence, but to be
of practical use, fluorescent dyes must satisfy
certain requirements: they must produce a pure
color dictated by their absorption and emission
spectra, they must have a high molar extinction
(high absorption), and most important, they
must have a high quantum yield. These requirements are met by few dyes. A disadvantage
shared by many fluorescent dyes is their poor
lightfastness, but there are some exceptions.
In this article some of the most important
fluorescent dyes and their applications are
described. For a general discussion of the properties of organic dyes and pigments, see !
Dyes, General Survey; ! Pigments, Organic.
2. Naphthalimide Dyes
A very wide variety of naphthalimide dyes are
known (! Naphthalimide Dyes and Pigments).
Only a few important representative examples,

which show exceptionally brilliant, greenishyellow fluorescent colors, are discussed in this
section; most of them show poor lightfastness.
Brilliant Sulfoflavin FF (1), C.I. 56205 [239130-2] serves as a dye for wool and polyamides
[6]. Solvent Yellow 44 (2), C.I. 56290 [247820-8] is used to dye plastics and is of some
importance in the production of fluorescent
pigments [7].
Compound 1 is prepared from p-toluidine
and 4-amino-3-sulfo-1,8-naphthalic anhydride
[52173-68-9] which is obtained by sulfonating
4-amino-1,8-naphthalic anhydride. The production of (2) involves the reaction of
4-chloro-1,8-naphthalic anhydride with mxylidine, followed by the use of ammonia to
substitute the chlorine atom with an amino group.
groups on both nitrogen atoms as shown in the

structure below (4). The improvement in light
stability due to the introduction of the N-cyclohexyl group is utilized in the synthesis of
different light stabilizers of the hindered amine
families.
New naphthalimido- or naphthalimidylamino-substituted thiol derivatives were developed as fluorescent dye compounds, which are
useful for dyeing keratin fibers, especially for
lightening of dark human hair [9].
3. Coumarin Dyes
Many basic coumarin dyes found their applications as optical brighteners with intense fluorescence in the blue range. The structure of
some examples is given below, X might be H or
COO and R might be H, CH3, or CF3 [10].
4-Amino-3-sulfo-1,8-naphthalimide
is
being increasingly used to dye wool and Nmethyl(4-methylamino)-3-sulfo-1,8-naphthalimide [54229-25-3] to dye polyamides. Compound 3 [23741-82-4] is a reactive dye which is
employed to dye cellulose fibers [8]. Similar
water-soluble dyes are employed to dye silk and
are used in fluorescent flaw detection.
One more light-stable member of this dye
family is a naphthalimide dye with cyclohexyl
Many of these basic coumarins such as 7diethylamino-4-methylcoumarin (Coumarin 1)

are applied also as laser dyes [11].
Different coumarin derivatives can be produced by Pechmann condensation of phenols
with b-keto esters. Heat can be supplied conventionally or by microwave irradiation [12].
Dyes derived from coumarin, 2H-1-benzopyran-2-one [91-64-5], are usually intensely
colored, brilliant greenish-yellow dyes with
high quantum yields and high molar extinctions. They are moderately lightfast.
The most important fluorescent coumarin

dyes are derivatives of 7-dialkylaminocoumarin, which has a heterocyclic residue at
the 3-position (6).
Fluorescent coumarin dyes are used as disperse dyes for polyesters and polyamides, their
sulfonic acid derivatives are employed for dyeing polyamides, and their cationic derivatives
are used for dyeing polyacrylonitriles. Some of
these dyes are important as laser dyes or are
used in the production of fluorescent pigments
(see Chap. 13).
Coumarin dyes are among others obtained
by reacting 2-hydroxy-4-dialkylaminobenzaldehyde with the nitrile (or acetate) derivative
of a heterocycle as in the following example:
The use of a nitrile derivative results in the

introduction of an imino group at the 2-position
of the coumarin ring, as in compound 7.
Hydrolysis occurs under the conditions
employed for dyeing, and the imino group is
replaced by oxygen, yielding the corresponding
coumarin derivative.
Some important 7-diethylcoumarin dyes
(compounds 815) are listed in Table 1. The
introduction of a nitrile group at the 4-position
of the coumarin residue gives the dye an orange
red or red color, as in compound 16 [70546-257], which is the 4-nitrile derivative of 10 [19].
Compound 16 is used as a disperse dye for

polyesters and produces a brilliant red color of
moderate lightfastness. A coumarine dye with
orange red fluorescence and moderate light
fastness is Solvent Red 197 [52372-39-1].
Substituted coumarins are successfully prepared in a one-pot synthesis catalyzed by silica
gel-supported sulfuric acid under solvent-free
conditions [20].
4. Xanthene Dyes
Fluorescein (17), C.I. 45350 Acid Yellow
73 [518-47-8] is the best known xanthene
dye (! Triarylmethane and Diarylmethane
Dyes).
Even a very dilute solution of this dye

exhibits an intense yellowish-green fluorescence. It is synthesized by reacting phthalic
anhydride with resorcinol. The eosines (bromine compounds) and erythrosines (iodine
compounds), phloxine B, C.I. 45410 [1847287-2], and Rose Bengal, C.I. 45440 [632-68-8]
are halogenated derivatives of fluorescein.
Eosin Y or Acid Red 87 [17372-87-1] is a
tetrabromo derivative of fluorescein, it is red
fluorescent and is available in cosmetic quality
as D&C Red No. 22.
Rhodamine dyes (aminoxanthenes) are a
very important class of xanthene dyes and
are of considerable commercial importance.
Table 1. 7-Diethylcoumarin dyes [1318]

Constitution
CAS registry number
Color
Use
Reference
yellow disperse dye
yellow for dyeing polyacrylonitrile, fluorescent

pigment
yellow disperse dye, laser dye
yellow for dyeing polyamide
yellow disperse dye
[62143-26-4]
yellow disperse dye
[28754-28-1]
yellow disperse dye
[55470-53-6]
orange for dyeing polyacrylonitrile
[27425-55-4]
[12221-86-2] (C.I. Basic Yellow

40)
[38215-36-0]
[34564-13-1]
They are intensely brilliant, blue-red, fluorescent dyes with very high molar extinctions and quantum yields and are used for
coloring inks, paper, and plastics. Their sulfonated derivatives are used to dye wool and
polyamides. Rhodamine dyes are also one of
the starting materials for the production of
red fluorescent pigments; some of them are
employed as laser dyes. The most important
rhodamine dyes are synthesized by reacting
3-dialkylaminophenols with phthalic anhydride. The carboxyl group of the product
may then be esterified.
The first of the rhodamine compounds to be
reported was Rhodamine B (18), C.I. 45170
Basic Violet 10 [81-88-9] [21], which is used in
fluorescent pigments.
Its applications might be questioned in the

upcoming years due to its high hazard potential
[22].
Rhodamine 3 B (the ethyl ester of Rhodamine B), C.I. 45175 Basic Violet 11 [239063-8], and Rhodamine 6 G (19), C.I. 45160
Basic Red 1 [989-38-8], have properties similar
to those of 18 [23].
The product of the reaction of 3-diethylaminophenol with benzaldehyde-2,4-disulfonic

acid is Sulforhodamine B (20), C.I. 45100
Acid Red 52 [3520-42-1] [24], which is

used to dye wool and polyamides. It is also
employed in the production of fluorescent
pigments, and as a laser dye.
The alkyl groups on the nitrogen atoms of

Sulforhodamine 101 (21) [60311-02-6] are less
flexible than those of Sulforhodamine B (20)
[25], and the molecule is thus more rigid. Dyes
of this type have very high quantum yields,
approaching 100%, and are used as laser dyes.
Compound 22 is used as a reactive dye for

dyeing cellulose fibers [26].
The reaction of a coumarin dye with dicyanomethane produces 23, which can be considered as an azaxanthene dye [27].
intensely colored, lightfast, sublimate-free disperse dye. It is used to impart a yellow color to
polyesters [29] and is prepared by reacting
benzo[k,l]thioxanthene-3,4-dicarboxylic anhydride with aminomethoxypropane. If the latter
is replaced by stearylamine, Solvent Yellow 98,
C.I. 56238 [12671-74-8] is formed that is particularly useful for dyeing plastics in bulk,
mineral oils, fats, and waxes [30].
This compound is used as a disperse dye for

polyesters. It produces an intensely brilliant,
moderately lightfast, red color. Somewhat better lightfastness is found for the purer version,
especially useful for coloring engineering plastics and is known as Solvent Red 196, C.I.
505700 [52372-36-8].
5. Thioxanthene and Benzoxanthene

Dyes
The color of fluorescent thioxanthene dyes
ranges from yellow to red. These dyes are
usually less brilliant than the coumarin dyes
and the rhodamines, but some of them show
good lightfastness. The thioxanthene ring system is produced by means of a Pschorr ring
closure, as shown for Fluorescent Red GG (24),
C.I. Solvent Orange 63 [16294-75-0] [28]:
Plastics can be colored red with compound

24 which has a good lightfastness.
Samaron Brilliant Yellow H 6 GL (25), C.I.
56235 Disperse Yellow 105 [14121-47-2], is an
Compound 26 [18014-08-9] can be

employed as a disperse dye, with good lightfastness, to impart a brilliant pink color to
polyesters [31]. Compounds 25 and 26 are
also classified as naphthalimide dyes.
Disperse dye 27 [35763-62-3] and its isomer
27a give a very brilliant yellowish-red color
having moderate lightfastness when applied to
polyesters [32]. The naturally occurring dye
Iachnanthofluorone (28) [53766-48-6] is a
red fluorescent xanthene derivative that is
closely related to compounds 2527 [33].
Structures as 25 or 26, where an oxygen atom

is present instead of the sulfur atom are called
benzoxanthene dyes. Water-soluble homologues
are mentioned in the literature [34].
6. Naphtholactam, Hydrazam Dyes

and Homologues
Naphtholactam dyes have colors ranging from
yellow to red and are suitable for dyeing polyesters and, in some cases, polyamides [35].
Although they show excellent lightfastness,
these dyes do neither have the high molar
extinctions nor the quantum yields of, for
example, the coumarins. Naphthostyril [13000-7] (the lactam of 1-aminonaphthalene-8carboxylic acid) reacts with a weakly basic
aromatic or heterocyclic amine or with a
reactive methylene group (e.g., a barbituric
acid derivative) in the presence of phosphoryl
chloride in an inert solvent to yield naphtholactam dyes. Compound 29 [67880-03-9] is
obtained if the reaction is performed with 2cyano-4-nitroaniline [36], as shown below; this
compound produces a reddish-yellow color
when used as a disperse dye with polyesters.
The disperse dye 30 [58470-74-9] gives a

yellowish-red color with good lightfastness
when applied to polyesters [37]; it is especially
suitable for textile printing.
Compound 31 can be used to dye polyamides orange red with a high degree of lightfastness [38].
Polyesters can be dyed orange to red with a

high degree of lightfastness by using dyes
typified by compound 32 [39].
Very interesting homologues of this series

with high absorption and quantum yields can be
obtained by introducing the lactam functionality into the structure of perylene dyes, typified
by 33 [40]. The R groups represent long alkyl
chains.
Structure 34, shows the so-called hydrazam

dyes, like naphthalenehydrazamimides and
perylenehydrazamimides [41]. If n is 0, they
show orange and red fluorescence, if n is 1,
their hue is blue and they fluoresce red or near
infrared.
polyacrylonitrile and acid-modified polyester

fibers. Dye 38 is a fluorescent greenish-yellow
[44] and is synthesized by condensation of
1,3,3-trimethylindoline-2-ylidene acetaldehyde
[84-33-3] (Fischer base aldehyde) with 3phenyl-2-pyrazoline [936-47-0].
7. Azlactone Dyes
Azlactones are formed by condensation of
benzoylglycine (hippuric acid) with an aromatic aldehyde in the presence of acetic anhydride and sodium acetate.
Dye 39 is formed by coupling diazotized ptoluidine to 1,3,3-trimethyl-2-(3-chloro-1-propylidene)indoline [45]. This product imparts a
fluorescent, lightfast, orange color to polyacrylonitrile.
Although azlactone dyes of the donor-acceptor

type (35) are very brilliant, they are not lightfast.
However, the greenish-yellow disperse dyes (36)
[25744-09-6] and (37) [51202-86-9] can be effectively used on polyesters. They possess excellent
coloring power and lightfastness [42, 43].
Another methine dye (40) [23406-34-0] colors polyacrylonitrile a brilliant red, but with
only moderate lightfastness [46].
8. Methine Dyes
Methine dyes (! Methine Dyes and Pigments)
are cationic dyes that are used to color
Dye 40 is formed by the condensation of

1,3,3-trimethyl-2-methyleneindoline with 4(N-methyl-N-cyanoethylamino)benzaldehyde.
10
9. Oxazine and Thiazine Dyes

Oxazine dyes (! Azine Dyes), such as Basic
Blue 3 (41), C.I. 51004 [63589-47-9], are used
predominantly to color polyacrylonitrile

greenish-blue [47]. Some of these dyes, including 41, are employed as laser dyes [48].
spectrum. Its maximum absorption is shifted to

longer wavelengths in comparison with stilbene
systems due to its more extensive conjugation. It
is used as a direct dye for coloring cellulose fibers
greenish-yellow.
Disperse Yellow 77 (45), C.I. 70150 [2228118-1] [51], can be prepared by acylation of 1aminoanthraquinone with acetic anhydride, followed by condensation with anthranilic acid
and zinc chloride at 100110 C. Both steps are
carried out in the same reaction vessel.
Thiazine dyes, e.g., dye 42, exhibit fluorescence at long wavelengths from 650 to 680 nm
and are also used as laser dyes.
Some dioxazines are also fluorescent dyes;

dye 43 imparts a fluorescent, yellowish-red
color to polyamides [49].
10. Miscellaneous Fluorescent Dyes

Diphenyl Brilliant Flavine 7 GFF (44), C.I. Direct
Yellow 96 [61725-08-4] [50], can be regarded as
an optical brightener (! Optical Brighteners)
which absorbs light in the visible region of the
Compound 45 is a brilliant, fluorescent,

disperse dye that can be used to dye polyesters;
it produces a greenish-yellow, sublimation-fast
color with especially good lightfastness.
Fluorol 242 (46), C.I. 68410 [6871-92-7], a
derivative of anthraquinone [52], is synthesized
by replacing the bromine atom of 4-bromo-6aminoanthrapyrimidine with an octadecylamino residue, followed by acylation with
butyric chloride. Compound 46 is a fluorescent,
yellowish-green dye and is suitable for dyeing
fats and oils [30].
Solvent Green 5 (47), C.I. 59075 [2744-505], is a heat-resistant, lightfast dye [53]. It is
used to color thermoplastic materials yellow in
bulk and is suitable for material testing (see
Chap. 12).
Solvent Green 7 or Pyranine (48), C.I. No.

59040 [6358-69-6], showing pyrene structure,
is often used in applications like text markers
and is also available in cosmetic grade (D&C
Green No. 8).
11
industrial applications like data storage and

energy transfer. Structure 50 shows terylene
diimides (n 2) and quaterylene diimides
(n 3) [55]. In other extended core perylenes,
A is representing different aromatic core extensions of the known perylene structures [56].
Perylenediimide dyes with O-aryl substituents in the bay region [57] are technically
important as colorants for engineering plastics.
The O-aryl substituents prohibit the general
tendency of aggregation of perylene diimide
dyes, which is attended by fluorescence
quenching. Similar persistent fluorescence of
perylenediimide dyes is caused by steric inhibition of aggregation [58, 59]. The reported
dyes either exhibit branched alkyl chains
with no substituents in the bay region (R
H, methyl, ethyl, O-aryl replaced with H) or
have small substituents at the N atoms combined with substituted O-aryl groups, see structure 51. Unsymmetrical substitution is also
known for both regions.
Perylenetetracarboxylic acid diarylimide

derivatives typified by 49 [54] are used in the
bulk dyeing of plastics (! Naphthalimide
Dyes). They produce extremely lightfast, red
colors and are suitable for the production of
fluorescent collectors (see Chap. 11).
Interesting fluorescent homologues of perylene diimide dyes, some fluorescent in the

infrared region, were developed for novel
The vat dye Thioindigo Red B (52), C.I.

73300 [522-75-8], is not fluorescent. However,
this substance and its derivatives can be used
conveniently in the bulk dyeing of plastics.
They dissolve in the plastic material producing
lightfast, heat-resistant fluorescent colors [60].
Asymmetrical thioindigo derivatives are
12
suggested as especially suitable for the bulk

dyeing of polyesters [61].
Azo coupling of 5-nitro-2-aminoindazole to

2,4,6-tris(N-dimethylamino)pyrimidine yields
Azo Orange (58). Compound 58 is not fluorescent, but is converted to the yellow fluorescent
dye 59 [38432-19-8] by treatment with acid [67].
Compound 59 can be used as a disperse dye to
impart a lightfast, yellow color to polyesters. The
formation of 59 from 58 illustrates that the stiffening of a molecular structure can convert a nonfluorescent azo dye into a fluorescent system.
For a detailed study of the fluorescence of

indigoid dyes see [62] and for syntheses and
examinations of different Oxindigos (53) see
[63, 64].
Diketopyrrolopyrrole (DPP, 54) pigments
like Pigment Orange 73 or Pigment Red 254
lose their pigment character, when long alkyl
chains or alkyl-substituted phenyl groups are
attached to the DPP core. A variety of representative fluorescent dyes of this group was
synthesized and is utilized in industrial applications. A comprehensive report on fluorescent
diketopyrrolopyrroles can be found in [65].
The naphthyridine dione dye Ciba Lake Red

B (57), C.I. 73095 [6417-51-2] [66], was also
recommended for the bulk dyeing of plastics; it
produces red fluorescent shades. This dye is
synthesized by the acylation of indigo with
phenylacetyl chloride and ring closure.
In addition to the presence of single chromophores in fluorescent molecules many compounds were synthesized, which utilize single
chromophores as monomers to create a wide
range of light-emitting oligomers, polymers, diades, triades, dendrimers, hyperbranched polymers, and self-assembling structures. Some of
them include dyes of different absorption wavelengths and can be tuned in order to absorb the
light from short wavelength regions, to concentrate all the harvested light and to convert it into a
red or near infrared emission [6871].
11. UV Fluorescent Chromophores

with No or Low Body Color
Dyes, which have their hue only under UV-light,
are of high interest for security applications. The
major amount of these dyes remains unpublished
for good reasons. Still the general principle of
those dyes is a high Stokes shift between the
absorption wavelength and the fluorescence

wavelength, enabling the absorption and activation of the molecule under UV light, emitting
afterwards blue, green, yellow, orange, and red.
Interesting benzazole derivatives showing such
properties are shown in structure 60, where X
might be O, S, or NH [72].
12. Special Uses

The general uses of fluorescent dyes as colorants
for fibers and plastics have been described in the
preceding sections. This chapter describes special applications of fluorescent dyes, but does not
include their use as laser dyes [73] (! Laser
Dyes). Daylight fluorescent pigments are treated
in Chapter 13. Daylight Fluorescent Pigments.
Photochemistry. A variety of fluorescent
dyes, in particular xanthene dyes (e.g., Rose
Bengal), are used as sensitizers in photochemistry [74].
Material Testing. Fluorescent dyes, e.g.,
Solvent Green 5 (47), are used in the testing
of materials to detect microflaws in the surfaces
of metals.
Fluorescent Collectors. The principle of
solar collectors is not new, the first plates
were mentioned in 1969 [75]. Fluorescent collectors consist of highly transparent plastic
sheets, e.g., poly(methyl methacrylate), which
are colored with a fluorescent dye. Exposure of
the sheets to diffuse sunlight produces fluorescent light, which is then concentrated and collected by total internal reflection and released
from the thin surfaces at the edges of the sheets.
The collected light energy can be used to
produce electricity by means of solar cells
(! Solar Technology) [76]. The advantage of
using solar collectors in combination with solar
cells is of importance when daylight is diffuse
like in the winter period in middle Europe. Dyes
showing perylene diimide structures, typified
by 49 have proved to be most useful for this
13
purpose. Aggregation problems e.g. of the

orange fluorescent perylene dyes without any
substituents in the bay region, have been
encountered by the introduction of bulky
groups at the nitrogen atoms [58, 59].
Indicators. Fluorescent dyes are used as
indicators in analytical titrations (! Indicator
Reagents).
In precipitation titrations, the fluorescent
dye is adsorbed to the surface of the precipitate
and undergoes a clearly recognizable change in
fluorescence at the end point. Silver ions can be
titrated in this way, using fluorescein (17) or
Rhodamine 6 G (19) as an indicator.
Another class of fluorescent indicators consists of water-soluble compounds whose fluorescence changes at the end point. These
indicators permit the titration of turbid or colored solutions. Thiols, for example, can be
titrated with organic mercury compounds using
fluorescein as an indicator.
Derivatizing Reagents. Substances that are
normally very difficult to detect (amines, amino
acids, peptides, sugars, carboxylic acids, and
lipids) can be converted into their fluorescent
derivatives with a suitable reagent. The derivative is then separated by means of TLC or
HPLC and its fluorescence is measured. Detection sensitivity is very high; aniline, for example, can be detected at a concentration of 2 ng/
mL [77]. Examples of such reagents are given
in Table 2 (compounds 6165).
Compounds 64 and 65 are particularly interesting fluorogenic compounds because they
produce intensely fluorescent derivatives,
although they themselves do not fluoresce.
Fluorescent Probes. Fluorescent probes
permit measurement of various parameters in
cellular systems. For example, the pH can be
measured by treating thin tissue sections with a
fluorescent pH indicator, such as 4-methyl-7hydroxycoumarin (66) [90-33-5] (pKa 7.6) [78].
14
Table 2. Reagents used to synthesize fluorescent derivatives for chemical analyses

Name
CAS registry
number
Naphthyl isocyanate (61)
[86-84-0]
alcohols and amines
1-Dimethyl-5-naphthalene-sulfonyl chloride (dansyl

chloride) (62)
[605-65-2]
amines and phenols
Fluorescein isothiocyanate (FITC) (63)
[27022-45-3]
amines, amino, acids, and

proteins
1,2-Benzenedicarboxaldehyde (o-phthalic anhydride,

OPTA) (64)
[643-79-8]
primary amines
N-4-(2-benzimidazoyl) phenylmaleimide (BIPM)

(65)
[27030-97-3]
thiols
Other fluorescent probes are used to determine the partial pressure of oxygen, the membrane potential, the redox status, the degree of
lipophilicity, viscosity, etc. [79]. Interference
caused by the addition of foreign fluorescent
probes can often be avoided by exploiting the
intrinsic fluorescence of many natural products,
such as thiamine [80]. Test strips coated with
fluorescent probes have attained considerable
importance in medical diagnostics [81]. For
example, theophylline in serum may be determined by this method. Fluorescence-based
immunoassays have also been developed (!
Diagnostic Reagents).
Structural formula
Derivatized compounds
Enzyme Substrates. Enzyme activity can

be measured by allowing enzymes to act on a
substrate to produce an intensely fluorescent
product. Suitable substrates are provided by the
carboxylic acid esters, phosphates, and sulfates
of highly fluorescent phenols with pKa values
between 6 and 9 such as 4-methyl-7-hydroxycoumarin (66), fluorescein (17), and 2hydroxy-3-naphthoic acid (67) [92-70-6].
The glycosidic ethers of these phenols

formed with a variety of sugars (e.g., glucose
and galactose) are important in determining the
activity of enzymes that cleave sugars.
Esters formed from compound 66 and longchain fatty acids are commercially available
and are suitable for measuring the activity of
carboxyl esterases. The palmitic acid ester of
compound 67 exhibits very weak fluorescence
at 400 nm and is cleaved to palmitate and 67 by
the enzyme lipase. Since compound 67 fluoresces very intensely at 460 nm, the rate at
which the intensity of fluorescence increases
can be used to measure enzyme activity (direct
continuous kinetic assay) [82].
Oil Fluorescent Markers Naphthalimide
dyes with long alkyl chains found technical
importance due to their solubility in a variety
of organic compounds such as mineral oil,
polyalkylene glycols, polyol esters, and motor
oil [83]. In structure 68, the Z, Z0 substituents
are alkyl chains with most preferably 16 to 20
carbon atoms.
More advanced molecules of this category of

naphthalimide dyes are reported in [84]. Beside
the greenish yellow fluorescent naphthalimide
markers, a variety of other markers emitting at
longer wavelengths have been synthesized as
lipophilic fluorescent dyes.
15
fluorescent pigments consist of finely divided

resin particles that contain daylight fluorescent
dyes. Fluorescent toners or fluorescent melting
pigments have a distinct solubility, but they are
not solubilized by solvents in the final application and have a very low or negligible migration. Their luminosity and brilliance make them
particularly useful if intense or long-distance
visibility is needed.
Daylight fluorescent pigments absorb UV
and visible light from daylight and reemit it
at a higher wavelength as visible radiation. As a
rule, the time interval between light absorption
and emission is very short (108 s), and the
fluorescence persists only in the presence of an
exciting light source. These pigments should
not be confused with UV fluorescent pigments,
which only fluoresce under UV light, or with
phosphorescent pigments, which continue to
emit light in the dark.
13.1. Production
Most daylight fluorescent pigments are composed of one or more fluorescent dyes and a
solid dye-carrying substrate or matrix. Optical
brighteners, UV absorbers, or ordinary pigments (e.g., phthalocyanines or titanium dioxide) are sometimes also included. The matrix
has a high affinity for the dye, thereby protecting it from environmental hazards. Fluorescent
pigments can be prepared by adsorbing fluorescent dyes onto the surface of fine silica gel
particles [85], but selected grades of polymers
are usually used as matrices. End of the 1990s
more advanced mechanically resistant structures have been prepared, consistent of silicon-based sol/gel glass as an inorganic
carrier. Covalent bonding between perylene
chromophores and the guest silicon-based carrier results in right robust and finely dispersed
emitting particles [8688].
13. Daylight Fluorescent Pigments
13.1.1. Dyes
Pigments
for
Daylight
Fluorescent
Pigments and dyes are distinguished from each

other by their solubility in the application
medium. Dyes generally are soluble in the
application medium, while pigments are practically insoluble, see also ! Pigments,
Inorganic, 1. General. Most daylight
Daylight fluorescent pigments are mainly

applied due to their peerless brightness, either
to obtain optimal brightness or in combination
with conventional pigments in order to brighten
applications with conventional colors.
16
99% of current fluorescent pigments are

solid solutions of fluorescent dyes in resins.
The pigment performance depends on the
resin (major impact), the dye, and the interaction, and the physical or chemical bonding
between the utilized dyes and the resins. Since
their market introduction, fluorescent pigments have always been stir-in pigments.
Despite this main advantage, older generations of fluorescent pigments showed different
disadvantages [89].
Many dyes exhibit daylight fluorescence,
but very few are useful for making pigments;
the most important are listed in Table 3.
The concentrations of the dyes in the matrix
range from ca. 0.1 to 10 wt %. Red fluorescent
xanthene dyes exhibit the highest emission
intensity at a concentration of ca. 0.5 wt %.
Yellow naphthalimide dyes may be added at a
concentration of up to 10 wt % without causing
appreciable quenching. The fluorescence
quenching and migration of the dyes out of
the carrier are much more difficult to influence
and to control at high dye concentrations. Mixtures of fluorescent dyes very often emit light at a
higher intensity than that produced by the separate dyes; this is due to sensitized fluorescence.
Sensitized fluorescence is one of the basic principles used in the production of fluorescent
pigments and occurs when a portion of the
excitation energy of one dye is transferred to a
second dye with similar electron energy levels.
The second dye is thus excited (sensitized) and
fluoresces. Bright fluorescent yellow, orange,
red, pink, and magenta shades are obtained by
mixing yellow, pink, and violet dyes.
At specific wavelengths, daylight fluorescent pigments reflect more light than a white
surface does at that wavelength. This is due to
the conversion of a portion of the absorbed light
to light at the hue-wavelength, which is emitted
additionally to the normal reflection of not
Table 3. Dyes for daylight fluorescent pigments
Pigment
CAS registry number
Color
Solvent Yellow 44 (2)

Solvent Yellow 160 : 1
Basic Yellow 40
Basic Violet 10 (18)
Basic Red 1 (19)
Acid Red 52 (20)
[2478-20-8]
[61902-43-0]
[12221-86-2]
[81-88-9]
[989-38-8]
[3520-42-1]
yellow
greenish-yellow
greenish-yellow
pink
pink
pink
absorbed parts of the illuminating light. As

can been seen in Figure 1, a theoretical white
surface reflects a maximum of 100% of the
incident light (practically around 97%),
whereas daylight fluorescent pigments can
show a total reflection of over 220 % at the
hue-wavelength. As a result, the visibility is up
to three times higher than that of a comparable
conventional not fluorescent hue.
Examples of pigment reflectance at different
wavelengths are listed in Table 4.
13.1.2. Pigment Matrices
Most fluorescent pigments are based on toluenesulfonamidemelamineformaldehyde resins that are prepared by bulk polymerization.
The fluorescent dyes are added at different
stages of the polymerization process. Further
reaction yields a highly cross-linked, colored
resin, which solidifies when cooled and is then
pulverized to give a fine pigment powder [90,
91]. The pigments may also be prepared by
emulsion polymerization, in which the colored
precondensate is further reacted after being
mixed at high speed into, for instance, a liquid
resin [92] or a molten wax [93]. This results in
the formation of spherical pigment particles.
Other matrices are based on benzoguanamineformaldehyde resins which are prepared
by emulsion polymerization in an aqueous
phase [94]. For further details of bulk and
emulsion polymerization, see ! Polymerization Processes.
Pigments based on polyamide [95] and polyester matrices [96] show high heat resistance.
Crystalline polyester resins suitable for producing fluorescent pigments [97] are called
melting fluorescent pigments and are mainly
used for coloring olefins.
Table 4. Spectrophotometric parameters of daylight fluorescent
pigments of the ARACO 10 series (ARALON GmbH, Germany) at
25% in acrylic resin at a film thickness of 12 mm
Color
Maximum emission
wavelength, nm
Reflectance, %
Blue
Green
Lemon
Orange
Red
Magenta
455
520
535
605
615
625
75
115
169
225
203
171
For radiation-curable fluorescent ink bases see

[98] ! Paints and Coatings, 3. Paint Systems,
Chap. 7. Radiation-Curing Systems. Advanced
fluorescent plastic colorants with very low plateout allow longer production runs on the injection
molders [99]. Nonplasticized poly(vinyl chloride)
and its copolymers [100], urethane resins derived
from isocyanates, and compounds containing
hydroxyl groups [101] have also been used as
pigment matrices. Acrylic-based fluorescent
nanoparticles were prepared by modifying different dyes, mainly perylene dyes with ethane
groups, which polymerize into the acrylic matrix
through radical polymerization [102].
17
bound dyes is overwhelming, looking on the

amount of submitted patents and publications,
which deal with this subject.
Cross-linked polymer particles containing
fluorescent dyes (Fig. 2) are reported in [106].
Claimed is a fluorescent pigment containing a
polymer matrix based on PMMA and an apolar
fluorescent dye of the coumarin or perylene
series. The matrix is a cross-linked poly(meth)
acrylate prepared by suspension polymerization.
The synthesis of polymerizable perylene3,4,9,10-tetracarboxylic diimides and their
polymerization in acrylic resins is reported
in [107].
13.1.3. Formaldehyde-Free and SolventResistant Fluorescent Pigments

Initially, formaldehyde-free fluorescent pigments have been developed mainly for coloring
olefins [103]. For this purpose, they need to be
heat-resistant, but high solvent resistance is not
required. Beside the above-mentioned polyester
resins [97], many similar carriers were utilized.
Recent developments are based on thermoset
polyesteramide chemistry. These formaldehyde-free pigments overcome the problem of
formaldehyde out-gassing, arising especially at
high temperatures. Possible applications are
plastic safety materials, rubbers, PVC, PU,
paints, and printing inks. Due to their low or
absent migration in PVC and PU, cosmetic and
noncosmetic grades of solvent resistant, formaldehyde-free pigments were developed [104].
13.1.4. Sunlight Sensors
A range of fluorescent pigments was developed
which fade at a controllable rapid rate in
response to light exposure. They can be used
to produce light exposure or fading indicators
which can be easily read with the naked eye.
Potential applications range from ensuring that
fluorescent safety materials have retained their
high visibility to the production of temporary
self-erasing markings [105].
13.1.5. Fluorescent Modifications with
Covalently Bound Dyes
The number of novel syntheses of fluorescent
particles and preparations based on covalently
Figure 2. Fluorescent dyes used in cross-linked polymer

particles [106]
18
Figure 3. Example of polymeric colorant [108]
Functionalized perylene-3,4,9,10-tetracarboxylic acid diimides are used as initiators and/or

coreactants for polymerization reactions. The
novel functionalized perylenetetracarboxylic
acid diimides and the use of the colored and/or
fluorescent polymers (Fig. 3) are reported in [108].
Novel liquid-crystalline poly phenylene
ether (PPE)naphthalene copolymers display
blue solid-state fluorescence [109].
Lyotropic polyamide carboxylic acid esters
with perylene dyes units in the main chain are
shown in Figure 4 [110]. The chromophores
were bonded to the polymer following the
newly developed shear approach and imidized
after orientation.
13.1.6. More-Not Resinated-Solid-State
Fluorescent Pigments
Very few pure crystalline pigments have daylight fluorescent properties, which are strong
enough for industrial applications. One example is the well-known Pigment Yellow 101,
C.I. 48052 [2387-03-3] shown in Figure 5 [111].
Other modifications of Pigment Yellow 101
were synthesized and examined [112].
The chemical structure of a mesoionic molecule [113], with bright yellow color, pigment
properties, and solid-state fluorescence is
shown in Figure 6.
A novel and interesting solid-state fluorescent perylene pigment with strong orange red
fluorescence is shown in Figure 7 [114].
While long alkyl chains are known from previous studies to increase the solubility of the
perylene chromophores attended by a decrease
of the pigment character of the molecules, short
alkyl chains support the pigmentary character.
Switchablesolid-statefluorescenceisdepicted
by fluorenone-based host compounds [115].
In addition to the above-mentioned variations
of solid-state fluorescent pigments, fluorescent
chromophores are reported, which lose part of
their substituents upon heating. Heat is applied to
decrease their solubility and restoring their pigment properties in some carriers [116].
13.2. Quality Specifications

of Fluorescent Pigments
Daylight fluorescent pigments are offered in a
series of colors with carriers having often the
same basic structure. Properties as color
strength, solubility, particle size, resistance to
solvents, light, and heat differ within the various groups. Sometimes, especially light stability and heat stability might differ within the
same group. Special series are available for
most applications to satisfy the specific requirements of processing techniques and formulations. Important factors in recent years concern
safety issues. Series showing low efflorescence
or migration of the low-molecular-mass fraction of the resin and no efflorescence or low
migration of the dyes are preferred.
Figure 4. Polymers with solid-state fluorescence [110]

19
20
Since the pigments are translucent, a white

undercoat is recommended for optimal brightness results. Light stability problems are countered in the final application via:
Figure 5. Chemical structure of Pigment Yellow 101
Figure 6. Mesoionic fluorescent organic yellow pigment

[113]

Adding UV absorbers
Using higher pigment concentration
Increasing the thickness of the application
Using a top coat, which includes UV
absorbers, and
Using more sophisticated coating systems
with special layers in addition to the UV
absorbing one
Long light stability to indoor light exposure
is generally given, especially for the highquality grades on the market.
13.3. Applications of Fluorescent

Pigments
Figure 7. Novel solid-state fluorescent perylene pigment

[114]
The right choice and development of the

suitable matrix for the utilized dye and application is the major quality distinction between
different available grades on the market. High
control of the production parameters and all
influencing parameters are required in order to
guarantee consistent quality and avoid application problems. Furthermore, the correct
choice of the right pigment for the right application is crucial and requests a high qualified
technical communication on all sides of the
supply chain.
Fluorescent pigments are generally fine
powders with a particle size of 210 mm.
They are easily dispersed in commonly used
binders, resin vehicles, and polymers. Due to
their nature, fluorescent pigments have always
been stir-in pigments, almost all available
grades do not require further grinding in the
final application, just mixing is sufficient to
obtain homogeneity and finely dispersed preparations. For offset printing or stationary
applications, submicron dispersions are available [117].
Fluorescent pigments are used where safety,

high visibility, security, and rapid identification
are important. Typical applications are the
marking of danger areas, aircrafts, ambulances,
naval vessels and buoys, safety clothing, traffic
signs and cones, and symbols on slow-moving
vehicles.
As a result of their striking visual impact,
daylight fluorescent pigments are used to
enhance a wide range of products (e.g., consumer goods, packaging, coated papers, and
textiles), as well as for publicity and advertising. As UV-responsive colors, these pigments
are employed in the coding and tracing of
documents, in theater scenery, in entertainment
decorations and in automating processes. The
wide demand for daylight fluorescent pigments
has resulted in the development of special
products for printing, coating, painting, cosmetic, and food contact applications. The use
of fluorescent pigments in the plastics industry
has almost unlimited possibilities.
Since the 2000s, a very wide utilization in
toys, detergent packaging, marker-pens, safety
jackets, sport clothes, and especially sport
shoes has been noticed. Cosmetic grades
have found their applications in traditional
cosmetic articles like lip sticks, nail varnish,
face and body painting.
13.4. Toxicology
Daylight fluorescent pigments are considered
to be nontoxic and are not radioactive. They do
not contain inorganic phosphorus, and heavy
metals are only found in trace amounts and are
not added intentionally. Most of the available
qualities fulfill the EN471 and the CONEG
requirements regarding heavy metal contents.
More penetration into the food contact plastic packaging applications and cosmetic applications should be carried out only with special
grades which are approved and tested for those
specific applications. As always, study of the
related technical data and safety data sheets is
of major importance.
References
General References
1 K. Venkataraman: The Chemistry of Synthetic Dyes, vol. 2,
Academic Press, New York 1952, pp. 740795.
2 P. Rys, H. Zollinger: Leitfaden der Farbstoffchemie, Verlag
Chemie, Weinheim 1970, pp. 87102, 113123.
3 Th. F
orster: Fluoreszenz Organischer Verbindungen, Vandenhoek und Ruprecht, G
ottingen 1951.
4 Th. F
orster: Umwandlung der Anregungsenergie, in W. Foerst
(ed.): Optische Anregung Organischer Systeme, Verlag Chemie,
Weinheim 1966, pp. 509552.
5 E. Lippert: Die Medienabhangigkeit der Fluoreszenzfarbe, in
W. Foerst (ed.): Optische Anregung Organischer Systeme, Verlag Chemie, Weinheim 1966, pp. 342355.
Specific References
6 General Aniline, US 2006017, 1932 (W. Eckert, W. Gmelin).
7 Hoechst, DE-OS 2423546, 1974 (Th. Papenfuhs).
8 Sumitomo, JP 44/15296, JP 69/15296, 1966 (H. Sugiyama, H.
Otsuka, M. Yamamato, T. Ikeda).
9 Oreal, FR 2912142, 2007, (A. Greaves, N. Daubresse).
10 A.N. Fletcher: Laser Dye Stability, Part 3: Bicyclic Dyes in
Ethanol, Appl. Phys. 14 (1977) 295.
11 M.R. Kagan, G.I. Farmer, B.G. Huth, Laser Focus 9 (1968) 26.
12 B. Rajitha et al., Arkivoc 2006 (xii) 2327.
13 Geigy, US 3014041, 1958 (H. Hausermann, J. Voltz).
14 BASF, US 3691187, 1970 (G. Grau).
15 Bayer, US 3985763, 1970 (H. Harnisch).
16 BASF, US 4055568, 1975 (M. Patsch, C. Vamvakaris).
17 Sumitomo, US 3704 302, 1969 (S. Enomoto, K. Sato, G.
Suzuki). Sandoz, US 4007188, 1972 (W. Koch).
18 Ciba-Geigy, US 3872132, 1970 (S. Koller, R. Zink, D. Reichel,
J. Voltz).
19 Ciba-Geigy, US 4547579, 1977 (P. Mockli). P. Mockli, Dyes
Pigm. 1 (1980) 315.
20 B.M. Reddy et al. Open Catal. J. 2 (2009) 3339.
21 BASF, US 377349, 1887; US 377350, 1887 (M. Ceresole).
21
22 R.P. Pohanish (ed.): Sittigs Handbook of Toxic and Hazardous

Chemicals and Carcinogens, 6th ed., Elsevier, Amsterdam
2012 p. 731.
23 BASF, US 516584, 1893 (H.A. Bernthsen).
24 Hoechst, US 1003738, 1906 (Emmerich).
25 Bayer, US 4100509, 1975 (H. Walther,W. Hartig, A. Friedrich,
R. Raue).
26 Hoechst, DE-OS 1955849, 1969 (F. Meininger, F. Kohlhaas).
27 BASF, US 4005111, 1976 (W. Mach, H. Scheuermann).
28 Hoechst, US 3829439, 1971 (E. Spietschka, J. Landler).
29 Hoechst, US 3367937, 1964 (O. Fuchs, H. Troester).
30 Chi-Kand Dieu: Solvent Dyes, in K. Venkataraman (ed.):
The Chemistry of Synthetic Dyes, vol. 8, Academic Press,
New York 1978, pp. 115120.
31 Hoechst, US 3502678, 1965 (O. Fuchs, H. Troester).
32 Hoechst, US 3781302, 1970 (O. Fuchs, E. Spietschka, J. Hohn,
H. Troester).
33 J.M. Edwards, U. Weiss, Phytochemistry 13 (1974) no. 8,
15971602.
34 Hoechst, GB 1518855, 1978.
35 H.R. Schwander, Farbensymposium 1976, Freudenstadt,
Germany.
36 M. Mostoslavskii, Ya. Shteinberg, C. Ivonina, I. Krutovskaya,
Zh. Prikl. Khim. (Leningrad) 51 (1978) no. 6, 14241426.
37 BASF, US 4009165, 1974 (E. Schefczik). Bayer, US 3980651,
1973 (A. Brack).
38 Bayer, US 3927005, 1973 (H. Harnisch).
39 Ciba-Geigy, US 4056528, 1975 (H.R. Schwander, K. Burdeska, Chr. Zickendraht).
40 H. Langhals et al., Angew. Chem. Int. Ed. Engl. 38 (1999)
201203.
41 Ciba, DE 69902818, 1999 (H. Langhals, R. Ismael).
42 BASF, DE-OS 2440405, 1974 (N. Zimmermann, E. Daubach,
H. Saukel).
43 Hoechst, DE-OS 2225546, 1972 (R. Schickfluss,
W. Steckelberg).
44 Bayer, US 4143228, 1969 (A. Brack).
45 Bayer, US 3770727, 1976 (H. Psaar, W. Kruckenberg).
46 Ciba, DE-OS 1936460, 1968 (A. Kaiser, W. Lang,
R. Jeanneret).
47 Bayer, DE 300253, 1916; Friedlander 13, 360.
48 Kodak, US 3731222, 1972 (K.H. Drexhage).
49 Ciba-Geigy, DE-OS 2506098, 1974 (H.R. Schwander,
A. Pugin, K. Burdeska).
50 Geigy, US 2684966, 1952 (E. Keller, R. Zweidler).
51 Bayer, US 3037836, 1959 (H.S. Bien, F. Baumann).
52 Bios 987 (1948) 174.
53 Bios 987 (1948) 187.
54 BASF, GB 1391543, 1971 (F. Graser). BASF, DE-OS 2210170,
1972 (F. Graser).
55 K. Mullen et al., Chem. Mater. 18 (2006) 37153725.
56 Ciba, WO 2000023446, 2000 (H. Langhals, S. Kirner,
P. Blanke, M. Speckbacher).
57 H. Quante: PhD Thesis, Universitat Mainz, Germany, 1995.
58 R. Ismael: PhD Thesis, Universitat Munchen, Germany, 1998.
59 H. Langhals, R. Ismael, O. Yuruk, Tetrahedron 56 (2000)
54355441.
60 Hoechst, US 3937666, 1970 (H. Schafer, E. Janousch).
61 Mitsui Toatsu, US 3963429, 1973 (M. Tsujimoto, K. Osawa,
I. Okubi). Ciba-Geigy, US 4304919, 1979 (N. Buhler,
H. Bosshard).
62 G.M. Wyman, Chem. Commun. 21 (1971) 1332.
63 B. Wagner: PhD Tesis, Universitat Munchen, Germany,
1995.
22
64 H. Langhals, B. Wagner: Oxindigo: Color Deepening, Strong

Fluorescence, and Large Stokes Shift by Donor-Substitution,
Angew. Chem. Int. Ed. Engl. 35 (1996) 10161019.
65 BASF, US 2009173916, 2009 (H. Yamamoto, N. Dan).
66 Ciba, US 1043682, 1912 (G. Engi). Allied Chemical, GB
1222314, 1968 (W.R. Demki, A.F. Lachlewski).
67 Geigy, US 3720671, 1968 (G. Kaupp). Hoechst, DE-OS
2355967, 1973 (E. Fleckenstein, R. Mohr). Hoechst, DE-OS
2360986, 1973 (E. Fleckenstein, R. Mohr). E. Bamberger, Ber.
Dtsch. Chem. Ges. 32 (1899) 1797; Justus Liebigs Ann. Chem.
305 (1899) 354.
68 M. Takahashi et al., Chem. Commun. 200630843086.
69 P. Hudhomme, J. Org. Chem. 73 (2008) 61426147.
70 K. M
ullen, F.C.De Schryver et al., Photochem. Photobiol. Sci.
2 (2003) 177186.
71 J.A.A.W. Elemans, A.E. Rowan et al., Adv. Mater. 18 (2006)
12511266.
72 C.M. Olando, J.G. Wirth, D.R. Heath, J. Chem. Soc. Chem.
Commun. 23 (1971) 1551.
73 F.C. Strome: The Dye Laser, Eastman Org. Chem. Bull. 46
(1974) no. 2, 14.
74 H. Meier: Photochemistry of Dyes, in K. Venkataraman
(ed.): The Chemistry of Synthetic Dyes, vol. IV, Academic
Press, New York 1971, pp. 494, 502504.
75 G. Keil, J. Appl. Phys. 40 (1969) 35443547.
76 W. Stahl, A. Zastrow, Phys. Unserer Zeit 16 (1985) 167179.
77 Y. Kanaoka, Angew. Chem. 89 (1977) 142152; Angew. Chem.
Int. Ed. Engl. 16 (1977) 137. J. Haugland: Covalent Fluorescent Probes, in R.F. Steiner (ed.): Excited States of Biopolymers, Plenum Press, New York 1983, pp. 2958. B.
Lingemann et al., J. Liq. Chromatogr. 8 (1985) 789874. G.
Schwedt: Fluorimetrische Analyse, Verlag Chemie, Weinheim,
Germany, 1981.
78 O.S. Wolfbeis et al., Fresenius Z. Anal. Chem. 314 (1983)
119127.
79 J. Haugland: Handbook of Fluorescent Probes, Mol. Probes
Inc., Junction City 1986.
80 O.S. Wolfbeis: Fluorescence of Natural Organic Products,
Part I, S.G. Schulman (ed.): Molecular Luminescence Spectroscopy, Wiley-Interscience, New York 1985.
81 A. Zipp, E. Hornby, Talanta 31 (1984) 863877. B. Walter,
Anal. Chem. 55 (1983) 498 A514 A. B. Walter, A.C. Greenquist, W.E. Howard III, Anal. Chem. 55 (1983) 873878. W.E.
Howard III, A.C. Greenquist, B. Walter, F. Wogoman, Anal.
Chem. 55 (1983) 878881.
82 G.G. Guiltbault: Enzymatic Methods of Analysis, Pergamon
Press, Oxford 1977. H. Bergmeyer: Methods of Enzymatic
Analysis, vol. 1 vol. 12, VCH Verlagsgesellschaft, Weinheim
19831986.
83 Dayglo Color, US 6248890, 1998 (W.R. Likavec, T.C.
Dipietro).
84 Radiant Color, EP 2166040, 2008 (R. Ismael).
85 Sherwin Williams Company, US 3518205, 1970 (M.S.
Vukasovich).
86 K. M
ullen et al., Am. Chem. Phys. 197 (1996) no. 38, 315.
87 K. M
ullen et al., Adv. Mater., 12 (2000) no. 5, 351354.
88 G. Schottner, Chem. Mater. 13 (2001) 34223435.
89 R. Ismael: Fluorescent pigments: applications shifting
towards safer and better performing products, Paint Coat.
Ind., 2010, August, 3437.
90
91
92
93
94
95
96
97
98
99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
117
Sterling Colour Ltd., FR 1321034, 1962.

Switzer Brothers, US 2938873, 1960 (Z. Kazenas).
Hercules Inc. (Radiant Color), US 4079026, 1978 (J.G. Mone).
Hercules Inc. (Radiant Color), US 3682854, 1972 (D.
Bennahmias, H.P. Locklin, P.G. Locklin).
Nippon Shokubai Kagaku Kogyo, DE-AS 2634415, 1976
(Tsubakimoto, Tsuneo, Fuzikawa, Iwao et al.).
Dayglo Color Corp., GB 1383051, 1972.
Hercules Inc. (Radiant Color), US 3922232, 1975 (A.K.
Schein).
Dayglo Color, US 5264153, 1993, (A.De Krom).
Dayglo Color, WO 9808915, 1996 (W. Likavec).
R. Ismael: New fluorescent pigments for plastics, Kunststoffe
International 4 (2007) 7677.
Hercules Inc. (Radiant Color), US 3796668, 1974
(R.T. Hickcox).
Siegle GmbH, US 3741907, 1973 (H.P. Beyerlin).
US Gov Sec Navy, WO 2009/134822, 2008 (J. Naciri,
C.M. Spillmann, G.P. Anderson, R.R. Banahalli).
Dayglo Color, WO 9743353, 1997 (W. Likavec, J. Waters).
Chanel Parfums Beaute, Radiant Color, WO 2011015906,
2009 (R. Ismael, H.De Clermont-Gallerande).
R. Ismael, Eur. Coat. J. 11 (2009) 3437.
BASF, EP 0692517 (US 5710197), 1995 (W. Fischer,
A. Deckers).
BASF, EP 0422535, 1989 (K.H. Beck, K.H. Ezbach).
S. Becker et al., US 2004024151, 2004.
H.F. Bunz et al., Chem. Commun. 2000, 8586.
C. Neuber: Chemistry and Processing of Poly(Amic Ethyl
Ester)s as Precursors for Highly Oriented Polyimides, PhD
Thesis, University of Bayreuth, Germany, 2003.
IG Farbenindustrie, DE 728303, 1940 (F. Mullbauer).
A. Dreuw et al., Molecular Mechanism of the Solid-State
Fluorescence Behavior of the Organic Pigment Yellow 101 and
Its Derivatives, Angew. Chem. Int. Ed. 44 (2005) 77837786.
Clariant, DE 102004003888A1, 2004 (T. Metz, C. Plueg).
H. Langhals, DE 102004024909A1, 2004 (H. Langhals,
O. Krotz).
J.L. Scott, T. Yamada, K. Tanaka, J. Chem. Res. (S) 2003, 483
484. New. J. Chem. 28 (2004) 447450. Chem. Commun. 2000,
8586.
Ciba Geigy, EP 0648817, 1994 (Z. Hao, J.S. Zambounis) and
cited literature.
Dayglo Color, WO 9631565, 1995 (J. Waters).
Further Reading
A.P. Demchenko: Introduction to fluorescence sensing, Springer
ScienceBusiness Media, New York 2009.
E.M. Goldys: Fluorescence applications in biotechnology and life
sciences, Wiley-Blackwell, Hoboken, NJ, 2009.
R.W. Sabnis: Handbook of biological dyes and stains, WileyBlackwell, Oxford 2010.
R.B. Thompson (ed.): Fluorescence sensors and biosensors,
Taylor&Francis, Boca Raton, FL, 2005.

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