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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
13.1.
13.1.1.
13.1.2.
13.1.3.
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
2. Naphthalimide Dyes
A very wide variety of naphthalimide dyes are
known (! Naphthalimide Dyes and Pigments).
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
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:
4. Xanthene Dyes
Fluorescein (17), C.I. 45350 Acid Yellow
73 [518-47-8] is the best known xanthene
dye (! Triarylmethane and Diarylmethane
Dyes).
Color
Use
Reference
[62143-26-4]
[28754-28-1]
[55470-53-6]
[27425-55-4]
[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.
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].
Compound 31 can be used to dye polyamides orange red with a high degree of lightfastness [38].
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.
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
10
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.
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).
11
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.
12
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].
13
14
CAS registry
number
[86-84-0]
[605-65-2]
[27022-45-3]
[643-79-8]
primary amines
[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
15
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].
13.1.1. Dyes
Pigments
for
Daylight
Fluorescent
16
Color
[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
Maximum emission
wavelength, nm
Reflectance, %
Blue
Green
Lemon
Orange
Red
Magenta
455
520
535
605
615
625
75
115
169
225
203
171
17
18
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].
20
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.
13.4. 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).
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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.