OPTICAL BRIGTENING AGENT

By:
Dr. Ruma Chakrabarti, Associate Professor, Kumaraguru College of Technology,
Coimbatore
Mr. A. Vignesh, Technical Compliance Manager, Hohenstein India Pvt. Limited.

Textile fibres do not appear perfectly white due to the presence of certain coloured impurities.
Whitening with optical brigthners or fluorescent brightening agents can eliminate the yellowish hue
of the materials. The optical brightening agents counteract the yellowness of the fabric by increasing
the reflection of the blue light rays. They convert invisible short wave ultraviolet rays of sunlight
into visible blue light and effectively neutralize the pale yellow or cream colour of the white
materials; hence a degree of whiteness, which is comparatively more intense, is achieved. The
greatest use of brighteners is in detergents, and almost every commercial detergent contains one or
more brighteners, in the proportion of 0.05-0.3%
The fluorescent substance to act as a whitening agent must essentially emit light in the blue region so
that it effectively neutralizes the normal pale yellow or cream colour of the so-called white materials.
OBA is based on the addition of light, whereas the bluing method achieves its white effect through
the removal of light. The optical brighteners should fulfill the following two requirements:
1. It should be optically colourless on the substrate

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 2. It should not absorb in the visible part of the spectrum.
The overall effect given by a whitening agent depends on a number of factors:
a) The intrinsic effectiveness of the compound as an OBA.
b) Its spectral absorption and emission characteristics.
c) The ultra-violet content of the viewing light.
Factors Influencing the functions of Optical Whiteners:
Optical brighteners are applied to substrate a s a separate after treatment process or are incorporated
into the bleaching and finishing baths. Since the fluorescent brightening agents behave like
dyestuffs, their efficiency and effectiveness are influenced by various factors that are important in
application.
Substrate: The brightening effect is dependent on the nature of the substrate. For e.g. A very strong
reflectance is observed whitened cotton, but is weaker in viscose and wool. In the absence of
sufficient affinity of brighteners, the application results in yellow to green colour yield.
Saturation: There is a saturation limit for each optical whitening agent. Above certain concentration
on the fibre a yellow colour is superimposed on the fluorescence resulting in decrease in whiteness.
Method of Application: The saturation limit of an optical brightening agent however is also
dependent on the method of application to the substrate. Usually exhaust application process gives
higher whiteness value than it does when applied by padding technique for a given amount of
whitener.
Time: Generally optical brightening agents have high rate of exhaustion on the substrate and
therefore great care is to be taken to avoid unlevel application. Slow exhaustion rate and increased
migration time is necessary to produce level whiteness on the fabric.
Temperature: The optimum temperatures of optical brightening agents on cellulosic fibres are
usually between 40 and 60 C and further rise in temperature tend to lower the exhaustion.
pH : The chemical stability, solubility and affinity of optical brightening agents depend on effective
pH value in solution.
Application of Optical Brightening Agents:

• Laundry detergents (to replace whitening agents removed during washing and to make

the clothes appear cleaner.) – detergents may contain up to 0.2% whitening agents,

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 • Paper, especially high brightness papers, resulting in their strongly fluorescent

appearance under UV illumination. Paper brightness is typically measured at 457nm, well

within the fluorescent activity range of brighteners. Paper used for banknotes does not

contain optical brighteners, so a common method for detecting counterfeit notes is to

check for fluorescence.

• Cosmetics: The brightener can not only increase the luminance and sparkle of the hair,

but can also correct dull, yellowish discoloration without darkening the hair. Some

advanced face and eye powders contain optical brightener microspheres that brighten

shadowed or dark areas of the skin, such as “tired eyes”.

• Fabrics may at times contain 0.5% OBAs. A side effect of the presence of OBA is to

make the treated fabrics more visible with Night Vision Devices than non-treated ones

(the fluorescence caused by optical brighteners can easily be seen with an ordinary black

light). This may or may not be desirable for military or other applications

Chemistry of Optical Brighteners

Optical brightening agents are generally based on compounds of stilbene, coumarins, pyrazolins,
naphthalimides, naphthooxazoles etc.
1. Carbocyclic compounds: Whiteners in this class have a high degree of whiteness
and specially suitable for use in detergents, plastics and Polyester substrates.
Stilbenes: These group consists mainly of non-ionic compounds, with general formula as shown
in (1) with an extended system of conjugated double bonds. They are chiefly suitable for
whitening of polyesters, and also polyamides, cellulose acetates and polyvinyl chloride.

R2
R1
(1)

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 Distyryl – Arenes: The non ionic class of distyryl-arenes are excellent whiteners for whitening
polyamides, cellulose acetates and plastics with a general formula (2). The anionic distyryl
arenes containing sulphonic acid groups are relatively high hypochlorite stable whiteners, which
exhaust on to cotton and polyamides when used in detergents. A further advantage of these
compounds is that in effluents the ethylene bridge is degraded in the presence of light and
oxygen leading to the formation of low molecular weight sulpho-carboxylic acids. Cationic
products serve for whitening cellulose, polyacrylonitrile and polyamides. They are especially
useful for application in detergent in the presence of cationic softeners.
R

R1 (2)
Where, R1 =2-CN, 4-CN, 4-SO2CH3, 2-CH3 etc
R2 = 2-CN, 4-CN, 4-SO2CH3, 2-OCH3 etc.

B= ,

Heterocyclic Substituted stilbenes, styrenes and ethylenes : The heterocyclic groups intensifies
the fluorescence of conjugated systems and shifts the fluorescence maximum to a longer
wavelength.
Stilbenyl benzoxazoles: This class consists of high light fastness whiteners for polyester. The
non-ionic stibenyl benzoxazoles (Fig. 3) are suitable for application by the HT or Thermosol
Process. They are also suitable for synthetic fibres such as polyamides or cellulose acetate.
Anionic stilbenyl benzooxazoles with sulphonic acid groups are whiteners fast to peroxide and
chlorine. They are suitable for cotton and polyamides, and for incorporation in detergents ( Fig.
4).

O R2
R'
N (3)

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 R2

O R3
R
N
n
R1 (4)
Styryl heteroarenes: The absorption and also the fluorescence of styryl heteroarenes are
hypsochromically shifted with respect to those of analogous stilbenyl heteroarenes. They are
less efficient and provide whiteness of lower intensity due to their lower molar and specific
extinctions.
The nonionic styryl heteroarenes with general structure 5 are suitable for fluorescent whitening
of synthetic fibres such as polyesters, polyamides and cellulose acetate.

R1 R2
(5)
Ionic Styryl Heteroarenes: only 4-naphtho[1,2-d]triazol-2-yl} -α - (benzoxazol-2-yl)styryls
with one or two sulphonic groups are known as anionic fluorescent whitening agents, and
cationic fluorescent agents of this group have the general formula :

R2 CH3SO3-

R1
n
(6)
Heteroarenes with one or two ethylene bridges:
a. Heteroaryl ethylenes and butadienes: The known whiteners in this class are
mainly nonionic. The 5-methyl-benzoxazol-2-yl ring plays an important role in whitening agents
for polyester. The polyester whitener based on the aforementioned ring has a very good light
fastness and also is easy to apply by both HT and thermosol methods, and as it sublimes easily
can also be used in transfer printing.
b. Non-ionic heteroarenes with two ethylene bridges: These are high-yield
polyester whiteners, also suited for whitening polyamides, cellulose acetates and

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 plastics such as polyvinyl chloride and polyolefins. Their synthesis is very
intricate, and the properties are comparable to that of carbocyclic distyryl-arenes.
c. Anionic heteroarenes with two ethylene bridges: These compounds contain
sulphonic acid groups and are high yield whiteners for cotton and polyamide, and
are suitable for application in detergents, textile and paper.
R2
B
1
R (7)
Triazinylaminostilbenes: 1,3,5,-Triazynyl derivatives of 4,4’- diaminostilbene –2-2’-disulphonic
acid are the most important class of whiteners in terms of volume. Triazinylaminostilbenes are used
for whitening cotton, resin finished textiles, regenerated cellulose fibres and polyamides. They are
also used in detergents to whiten textile and paper.

MO 3S
R1
N
NH N
N
R2
2 (8)
Heterocycles :
Furans and Benzofurans: Furans and benzofurans are useful building blocks in
combination with further cabocyclic and or heterocyclic systems for the synthesis of conjugated
fluorescent compounds. The most important classes are the phenylfuranyl and benzofuranyl-
benzimidazoles, which are characterized by their high degree of whiteness, good light fastness
and chlorite stability.
Benzofurans linked to carbocyclic group: Sulphonated derivative of the
compound with general structure (). Sulphonated derivatives of the above are used as whiteners
for cotton and polyamides.
Benzodifurans of the given structure with cyano or carboxylic ester groups have been suggested
as whiteners for polyester, polystyrene and polyvinyl chloride
O

O . (9)

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Heterocyclic substituted furans : non ionic products of this are used as whiteners for polyester
and polyacrylonitrile.
R2
R3
N
Anion-
O N
R
R1
(10)
Cationic heterocyclic substituted furans are used to whiten polyacrylonitrile and cellulose
acetate.
Heterocyclic substituted benzofuran: Non-ionic compounds of this group are used as whiteners
for polyester, polyamides, cellulose acetates and polyvinyl chloride.
Azoles : Mainly non-ionic whiteners have been obtained from this class of compounds. The
benzooxazole ring is easy to synthesize and has a good to outstanding light fastness property on
polyester substrate.
O
R1 R2
N (11)
Cationic azoles with the general formula as given below are used to whiten acrylic fibres.
Coumarins: The coumarin ring system substituted in the 3-position by (hetero) aromatic residues
or electron-attracting substituents is characterized by its high light stability.
Non-ionic Coumarins: These serve in particular for whitening polyester, but also for polyamides,
cellulose acetate, polyolefins and polyvinyl chloride.
R2

R1 O O (12)
Water soluble Coumarins: Cationic coumarins are used to whiten polyacrylonitrile and cellulose
acetate, and are characterized by possessing good light fastness and chlorite stability. The
cationic
residue may either be bound to a heterocyclic ring or to a basic side chain. Fibre-reactive
coumarins containing sulphonic acid groups are wash resistant whiteners for cotton and
polyamide.

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 +
N
N CH3
N

CH3OSO3-
N O
N O
N

H3C
(13)
Naphthalimides: The naphthalamide ring system has high stability with good light fastness and
chlorite stability, the only disadvantage being low molar extinction coefficient.
O
R1
N R2
2
R
O (14)
Non-ionic naphthalimides,: N-alkylated naphthalamides are especially used for polyester
substrate, but can also be used for whitening polyamide, cellulose acetate, polyolefins and
polyvinylchloride.
Water-soluble naphthalimides: Basic and cationic naphthalimides are chlorite-stable whiteners
for polyacrylonitrile with good light fastness. They are also recommended for whitening
polyester and wool.
Brighteners for Polyester Fibres:
These fibres require disperse dye type fluorescent brighteners due to their hydrophobic nature.
The brighteners enter the fibre in a state of molecular dispersion and are held in the fibre by Van-
der-Waals forces. The brighteners are usually water insoluble and can be applied in conjunction
with a carrier or in HTHP machine. Polyester brighteners belong to the group of compounds such
as stilbenyl benzo oxazoles, stilbenyl hetero arenes, heteroaryl ethylenes and butadienesdistyryl
arenes, Benzodifurans substituted with cyano or carboxylic ester groups,.non-ionic azoles,
naphthalamides etc.
Brighteners for Polyamide fibres: Fluorescent brightener of the acid dyeing coumarin type,
1,3-Diphenyl-2-pyrazolines, and of the stilbene- triazine types are widely used, besides the

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disperse type of synthetic-fibre brighteners. Water soluble anionic brighteners are applied like
acid wool dyes.
Brighteners for Cellulose: For cellulose brighteners with good penetrating properties, and of
medium substantivity are required . the brighteners for this category are distyryl arenes,
heterocyclic substituted stilbenes, styrenes and ethylenes., benzofurans linked to carboxylic
groups.
Ecological Aspect of Optical Brightening Agents:

One of the chemicals used for formulating a Optical brightening agent is called cyanuric

chloride, a derivative of 1,3,5 triazine. Cyanuric chloride is used as a precursor and crosslinking

agent in sulfonated triazine-stilbene based optical brighterners. It is also classified as “very

toxic”, “harmful” and “corrosive” by the EU and has several risk phrases identified with it –

including R26 (“very toxic by inhalation”). R26 is a substance which is specifically prohibited

by GOTS. Some of the OBAs are allowed, depending on the chemical composition of the

individual optical brightener. Like dyestuffs, GOTS allows optical brighteners if they “meet all

criteria for the selection of dyes and auxiliaries as defined in chapter 2.4.6, .” Those criteria

include the prohibition of all chemicals listed in 2.3.1 and substances which are assigned certain

risk phrases “or combinations thereof”.

Some brighteners have been proven to cause allergic skin reactions or eye irritation in sensitive

people. The German Textiles Working Group conducted a health assessment of various optical

brightening agents following concerns of potential health risks to the public. It was found that

there is a general lack of information on toxicity and a need for studies into dermal absorption

and the release of these substances from clothes. While it has not been shown to negatively

affect health, it has also not been proven safe.

These synthetic chemicals convert UV light wavelengths into visible light, which makes

laundered clothes appear whiter (although does not actually affect the cleanliness of the

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clothing). They've been found to be toxic to fish and to cause bacterial mutations. Further, they

can cause allergic reactions when exposed to skin that is later exposed to sunlight.OBA’s are

known to be toxic to fish and other animal and plant life and have been found to cause mutations

in bacteria.

Most OBAs are not readily biodegradable, so chemicals remain in wastewater for long periods of

time, negatively affecting water quality and animal and plant life. It is assumed that the

substances accumulate in sediment or sludge, leading to high concentrations.

REACH is the new European Union regulation which aims to improve human health and the

environment through better and earlier identification of the properties of chemical substances.

REACH stands for Registration, Evaluation, Authorisation and Restriction of Chemical

substances. REACH contains provisions to reduce the use of what are called “high volume

production” chemicals. These are defined as chemicals having annual production and/or

importation volumes above 1 million pounds. It is assumed that high volume production is a

proxy for high exposure; in addition, large releases of low toxicity substances such as salts do

cause environmental harm due to the sheer volume of the substance.

Much of the impact from optical brighteners comes in the form of large releases of low toxicity

substances. A number of these optical brighteners are listed as high and low production volume

substances and so will be subject to REACH.

In conclusion OBA is an auxiliary which enhances the aesthetic appeal of white fabrics but they

should be used keeping in mind their chemical constitution and hence its ecological and

environmental impact.

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