Fluorescent brighteners and optical whitening agents

W
hite textile articles become yellowish on storage. This undesired effect can
be removed as follows:

(1) By using chemical bleaching agent such as hypochlorite or peroxide. In this

method, there are chances of spoiling coloured goods and damage the fiber.

(2) By using small amount of blue colouring matter, which absorbs yellow light
and due to this yellowed fabric appears white.

(3) By using fluorescent compound which absorbs ultra violet light and converts
the energy into visible light of higher wavelength. In this way, a yellow
appearance can be corrected by the emission of a corresponding amount of
blue-violet light by the fluorescent compound. The effectiveness of fluorescent
agent depends on the presence of ultraviolet light in the illuminant.

The first use of fluorescent compound to whiten textile materials was,

described by Krais in 1929, but it has been commercialised only in 1940. Many
brightening agents have been described in patent literature, and used commercially.
They are sold in different names such as Blankophor (FBY), Calcofluor (ACY),
Fluolite (ICI), Leucophor (S), Photine (HWL), Pontamine White (DUP), Tinopal (GY),
and Uvitex (Cac, Ciba). As a class, they are termed fluorescent or optical whitening
or brightening agents.

By far the greatest use of brighteners is in detergents, and almost every

commercial detergent contains one or more brighteners, in the proportion 0.05% to
0.3%.
 Brighteners are also used in textile processing and the manufacture of paper.
They are also used in plastics, waxes, polishes, cosmetics and in hair rinse. They are
also used in the manufacture of synthetic fiber of all types.

For fluorescent substances to act as brightening or whitening agents, the

emitted light must be essentially blue light so that it effectively neutralises the normal
pale yellow or cream colour of so called white materials. In practice the dominant
wavelength of the emitted light must be around 450mµ.

Optical brightening is based on an 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.

(i) It should be optically colourless on the substrate and

(ii) It should not absorb in the visible part of the spectrum.

Since the fluorescent light of an optical brightener is itself coloured, i.e. blue
to violet or, sometimes, a bluish-green cast.

The overall effect given by a whitening agent therefore depends on a number

of factors.
(i) Its intrinsic effectiveness as a fluorescent.
(ii) Its spectral absorption and emission characteristics.
(iii) The ultra-violet content of the viewing light.
(iv) The self-colour of the substrate.
(v) The concentration on the substrate, which will of course depend on the
substantivity of the whitener for the substrate, and on the method of
application.
(vi) The physical form of the whitener on the substrate: the shade given by a
fluorescent on nylon, for example, is normally much more violet than the
shade on cotton.
Chemical Constitution

Stilbene derivatives
Most water
soluble brighteners
for the textile
materials are stilbene derivatives, and bistraizinyl derivatives of 4,4'-diaminostilbene-
2,2' disulphonic acid are of special interest. One of the early brighteners
manufactured by IG was 4, 4' bis (phenyluereido) stilbene 2, 2' disulphonic acid,
obtained by reaction of 4, 4' diaminostilbene - 2, 2' disulphonic acid with phenyl
isocyanate in aqueous medium. It was marketed as Blankophar R. (I).

The usefulness of this product is limited by its instability in a boiling bath.

Present
day commercial
products are of
the same general
types as
Blankophor B with
varing
substituents on
the tiazine ring.

In a similar
manner a number of other optical brightening agents of this type (CC/DAS) can be
prepared.

The principal effect of these

variations are changes in solubility, affinity, acid
fastness, etc. The class of bistriazinyl
compounds, in solution, is not fast toward
hypochlorite; some compounds, however,
show a certain amount of stability after
application to the fiber. The bistraizinyl
brightners are employed principally on
cellulosics, such as cotton or paper. Some
products also show affinity for nylon at the
weakly alkaline pH of most of the commercial detergents.
 By coupling diazotised
4-aminostilbene-supphonic acid
with 2-aminoaphathalene-6-
sulphonic acid and oxidising the
product with alkaline
hypochlorite a compound is obtained with structure (III; X=SO3Na, Y=SO3Na); it can
be added to a detergent as a brightner and has an advantage over many other
stilbene derivatives in that it remains effective in presence of bleaching agents.

Unsulphonated agents such as (III; X=CN, Y=H) can be applied as brightners

for synthetic fibres or plastic materials; other such as (III; X-SO2OPh or SO2N (alkyl)2
Y=H) are said to be suitable for similar purposes and also for application to oils, fats
and waxes. Cationic groups such as SO2NHC2H4NMe2 can be used to confer affinity
for polyacrylonitrile fibers.

Derivatives of dibenzothiophene-5, 5-dioxide

A further group of
brightners, which has been
studied primarily by American
Cyanamid, was found in the
derivatives of 3, 7- diaminodibenzothiophene-2, 8-disulfonic acid 5, 5 dioxide IV.

These compounds are relatively weak in comparison with stilbene derivatives

and give a greenish fluorescence. However, they do show good fastness to
hypochlorite.

Azoles (derivatives of 5-membered-ring heterocycles)

Monoazoles

The group based on

compound V arose from efforts
to find hypochlorite stables
compounds with neutral fluorescence, and was patented by Geigy. With warer-
solubilising group these types of compounds are suited to brightening cellulosic
materials or nylon from soap and detergent baths. Water insoluble derivatives of this
family, e.g. compounds having sulfamyl, arysulfnate, or nitrile groups, are suitable for
brightening synthetic fibers and resins.

Blankophor WT, has been proposed as a brightner in the dyeing of wool from an acid
bath. This compound is not effective in the presence of soap or synthetic detergents.

Bisazoles

Bisnaphotriazzolyl
compounds of structure VI are
obtained by coupling
tetrazotised amino compounds
with 2 moles of a
naphthyamine derivative
coupling in ortho-position,
followed by oxidation. These
products have good
hypochlorite stability.
Compounds of structure VII
are combinations of azoles
with napthotriazoles.

These compounds posses good fastness to hypochlorite and show mostly a red-
violet fluorescence.

Coumarin Derivatives
The optical brightening of
textile fibers by fluorescent
compounds was mentioned by
Krais. By treatment of flax with
esculin, a glucoside of esculeting
(VIII) a brightening effect was
achieved, but this effect was not
fast to washing and light. Later the
use of β-menthylumbelliferone (IX)
and similar compounds as brightners for textiles and soap was patented. As an
improvement over β-menthylumbelliferone, 7-aminocoumarin were proposed. These
latter are used for brightening wool and nylon either in soap powders or detergents or
as salts under acid dyeing conditions.

A further development of the coumarin group consists in the use of

derivatives of 3-phenyl-7-aminocoumarin (x). These compounds displace the hue
towards more neutral shades and, at the same time, significantly improve the
lightfastness. Brightners of this type are suitable by synthetic fibres and plastics.

Coumarin derivatives
substituted at position 3 by an aryl
radical and 7 by a group such as
ureido or a substituted triazinylamino
group Fig. XI, XII are of special
interest in that they can be applied
to fibers of cellulose, wool,
polyanide, polyurethane, cellulose acetate of polyacrylonitrile by dyeing processes or
to inert fibers such as polyesters by incorporation in the melt. They have good
fastness to light and impart a neutral white appearance to treated fibers.

Derivatives of 6-membered-ring
heterocycles

A further class of brightners is

derived from pyrazine. These
compounds may be employed for
brightening wool and various synthetic
fibers from a weakly acid to neutral
bath or from soaps and synthetic
detergents.

Derivatives of pyrazoline

Knorr discovered this Class of

optical brightening agents. It displays
intensive blue fluorescence and high
affinity and substantivity for the fibers.
 Optical brightening agents based on this group are used mainly for the
surface brightening of polyamide, acetate and polyacrylonitrile. They are unstable
against oxidants.

Finishing of Commercial Optical Brightners

Optical brightners may be obtained as powders, pastes, liquid water-soluble

forms or stable dispersions.

Pastes

Pastes are prepared from wet cake with various additives such as sodium
chloride, sodium sulphate, urea, etc. in a mixer.

Powder

The powder form is produced from above paste and dried in spray drier. The
powder are produced either diluted i.e. with additives or as concentrates where the
content of additive is low or completely absent.

Instant finish (easily water soluble)

Lately "instant" finishing has been used in the preparation of powders. It

involves converting poorly wettable powders of optical whitening agents into easily
wettable or soluble material, which is also non-powdering during addition. For
achieving the "instant" finish, optical brightening agent wetted powder is submitted to
a mechanical treatment during which individual powder particles are brought into
contact, stick together agglomerate to fine beads, which dried in spray drier.

Liquid forms

The most common liquid forms involve the preparation directly from the final
product.

Liquid forms are solutions of optical brightening agents which are completely
miscible with water. Both soluble and insoluble brightening agents are used in such
preparations, and they are brought into solution either by dissolution in a solvent, or
by chemical processes, in which the brightening agent is converted into the salt of a
soluble quaternary base. The second type of liquid form is prepared most frequently
from water-soluble derivatives of 4, 4'-diaminostilbene-2, 2' -disulphonic acid. A paste
or the dry product is acidified and the acid paste is dried and suspended in an excess
of amine and required concentration adjusted by water and quaternisation is carried
out with the hydrotropic substance.

A hydrotropic substance monoglycols diglycols or triglycols, glycerol, various

sugars, sulphite mother liquors, easily water-soluble amides, mono-alkanolamines,
dialkanolamines, trialkanolamines, urea and urethanes are used.

The liquid forms contain 10 to 40% active substance and 25 to 60%

hydrotropic substances; based on the weight of solid brightening agent.

Table 3:

Hydrotropic substances used in Optical Brightening Agent

Commercial Name Hydrotropic Substances

Albaphan CBS flussig deithylene glycol
Blankophor flussig urea, ammonia
Blankophor BBU flussig urea, ammonia
Blankophor BBH flussig urea, ammonia
Blankophor BE flussig urea, diethylene glycol
Blankophor BA flussig urea, ammonia
Blankophor RA flussig urea, ammonia, diethylene glycol
Blankophor CI flussig oxyethylated phenol
Celumyl CSP flussig ethanolamine, diethylene glycol
Fluolite MP liquid diethylene glycol, ethanolamine
Leukophor AC flussig diethylene glycol, tamol
Leukophor BS flussig urea, ammonia
Tmopal CH 3632 diethanolamine
Tinopal UP liquid ethanolamine, ethylene glycol
Tmopal 2BF flussig diethanolamine
Tmopal 4BM flussig triethanolamine, urea
Tmopal LAT flussig oxyethylated phenol
Uvitex PRS fluss, konz triethanolamine, urea

Stable Dispersions

Stable dispersion of optical whitening agent is prepared by utilising suitable

non-ionic dispersing agent. Disperse optical brightening agents are produced mainly
for the brightening of polyester fibers, cellulose acetate and polyacrylonitrile. The
aqueous dispersion of the optical brightner can be tinted with a blue dye. The
additional blue colouration of the dispersion brings about an increase in the
brightening effect up to maximum 30%.

Evaluation and testing

The evaluation of fluorescent brightening agents and assessment of their

practical performance are of prime importance to the user of these agents.
The main analytical tests applied to fluorescent brightening agents are designed to
determine the strength of fluorescent activity either in its own right or comparatively
against a known product and to establish the type of product and, if possible its
identity.

Active strength of fluorescent brightners

As all fluorescent brightening agents operate by absorption of ultraviolet light,

which can be used to measure the active fluorescent strength of a product. The
extinction coefficient of a solution of the fluorescent brightening agent at wavelengths
from 200 to 400 nm is determined by spectrophotometer. It can, however, be a
measure of active strength of a product, as the peak absorption at between 345 to
365 run is a direct measure of its active fluorescent strength. For cellulose
fluorescent brightening agents this is usually around 350 nm and the absorption at
this peak is used to calculate the extinction coefficient through a 1 cm cell at a
concentration of 1% weight/volume solution, usually expressed at E (1%1cm). This
value is used extensively in evaluation and standardisation, as a direct measure of
the fluorescent activity.

To establish the type of product, thin-layer chromatography is perhaps right

instrument.
Uses

The major consuming industry for optical whitener are as follows:

Detergent mixtures 40%

Paper 30%
Synthetic fibers and plastics 05%
Textiles 25%

Detergent Brighteners

Today scarcely a detergent exists which does not contain some cellulose
brightner. One of the principal requirements of such a product is that it has
satisfactory affinity in the presence of detergent. The brightening agent should have
satisfactory build up in multiple washing, but should not discolour the textile. In
addition, the product must be chemically stable to the other components of
detergents.

Detergent brighteners should have adequate lightfastness. The washed

textiles must not become discoloured in light. Certain brighteners can brighten the
detergent itself, so that the agent appears pure white.

Brighteners for the textile industry

Textile finishing requires brighteners of very good solubility and substantivity.

Mostly bistriazinyl derivatives of 4, 4'-diminostillbene 2, 2'-disulfonic acid are
preferred. Brightening agents must possess definite stability in combined processes.
The lightfastness of textile brighteners should be as high as possible. It is important
again that the brightener does not decompose to light in form coloured by-products.

The optical brightener should possess following properties to give best results.

(i) Substantivity for the fiber

(ii) Rate of strike
(iii) Build-up shade
(iv) Sensitivity to electrolyte
(v) Effect of temperature
(vi) Effect of pH of bath.

Textile can be divided as follows:

(a) Natural fibers, cellulose and protein fibers

(b) Synthetic fibers
(c) Mixed fiber blends

Natural Fibers

These are dealt with under two groupings

(a) Cellulose fibers
(b) Wool fibers

Brightener for cellulose

The brightening of cellulose fibers constitutes the most important use of

optical brighteners.

Cellulose yams in the form of crops, cheeses and beams can all be treated
with fluorescent brightening agents on package dyeing machines. The selection of
brightener and method of operation are of major importance in obtaining level
brightening. It is important with prepared packages, such as cops, cheeses and
beams, that the preparation should produce the most stable and permeable
construction.

Brighteners with good penetrating properties and of medium substantivity are

required to obtain even brightening for cellulose. These are two methods that can be
applied:

(a) Two-bath method, in which the brightener is applied to the fabric initially, then
dried and subsequently resin-finished.

(b) One-bath method, in which the brightener is applied in conjunction with the resin
finish by inclusion in the actual resin finishing bath.
 It is important to take into consideration the resin and catalyst combination.
The solution of fluorescent brightener should never be mixed with a strong catalyst
solution.

Brighteners for wool

The introduction of fluorescent brightening agents that can be applied to wool

enhances the whiteness but cannot achieve the brilliance of fluorescent.

The most common brighteners for application to wool are a select range of
dastriazinc derivatives with certain pyrazolene derivatives. The application is
invariably in conjunction with hydrosulphite, either alone or in the stabilised form.
Certain brighteners yield excellent results under these mildly acid conditions, while
others require an acid addition to exhaust them effectively onto the fiber.

Brighteners for synthetic fibers

Synthetic fiber can be divided as:

(i) Cellulose acetate

(ii) Polyamide fibers
(iii) Polyester fibers
(iv) Polyacrylonitrile fibers
(v) Acrylic fibers

Brighteners for Cellulose Acetate

Cellulose acetate show no affinity for the water-soluble cellulose brighteners

normally applied to cellulose, though they have some affinity for the soluble coumarin
type. Their main affinity if for the disperse dye type of brightener.

Acetate fiber can be brightened by a large number of compounds, such as

(aminocoumarin); (derivatives of 7-amino-3-phylecoumarin); (pyrazines);
(pyrazolines), provided the derivatives are water-insoluble; (bis (benzazoyl)
ethylenes). Brighteners for cellulose acetate can also be used in combination with
light-duty detergents.
Brighteners for polyamide fibers

Polyamide fibers and fabrics are produced from polyamide-6 and -66 type.
Fluorescent brighteners of the acid-dyeing coumarin type and of the stilbene-triazine
types are widely used, as well as the disperse type of synthetic-fiber brighteners.

In general, the easily water soluble products are preferred in textile

applications, but aqueous dispersions of difficulty soluble compound are also
employed. Water-soluble anionic brighteners are applied very much like acid wool
dyes. Polyamide brightening in the spinning mass ("Dope Dyeing") requires
particularly heat and reduction stable products.

Mainly das-triazine are the most widely used fluorescent brighteners for
polyamide-6 and -66 fibers. Most brighteners give better results when applied from a
bath containing a reducing agent which in itself is of advantage by acting as a mild
bleach.

Brighteners for polyester fibers

As a rule, polyester fibers require disperse dye-type fluorescent brighteners

due to their hydrophobic nature. These brightener particles penetrate into the fiber in
a state of molecular dispersion and they are held in the fiber not by polar affinity but
by Van der Waals forces. Polyester fibers show only very little swelling in water, ionic
processes are not assumed to be of importance for the movement of brightener in
the polyester fiber. The fitness of dispersion of the brightener particles is stabilised
by the addition of dispersing agents during manufacturing.

They are all water-insoluble products which usually must be applied in

conjunction with a carrier. The maximum in brightness and fastness is achieved only
by means of a final heat treatment. It is of fundamental importance for the brightener
to remain stable at the relatively high condensation temperature. Effective polyester
brighteners are compounds such as (biscbenzoxazoly) ethylenes; (naphthotriazolyl
stilbenes), and (derivative of 7-amino-3-phenylcoumarin).
 Fluorescent brighteners are applied to polyester fibers by exhaust processes
or by pad. Thermosol processes, the choice being dependent on the characteristics
of the material and the machinery available in the works.

The stability of the brightener dispersion within the fiber is of vital importance.

To ensure that the stability of the dispersion is maintained it is necessary:

(a) To dilute the dispersion with water at approximately 40"C just before it is
required.
(b) To control the build-up of temperature of the liquor.
(c) That any additional dispersing agent should be compatible and have protective
colloid effect.
(d) To avoid any auxiliaries that a cloud point, especially for high temperature
applications.
(e) To use no electrolyte and adjust pH with acetic acid; and
(f) Preferably to maintain acidity of the bath between pH 4 and pH 6.

Brighteners for Acrylic fibers

Acrylic fibers are extremely temperature-sensitive and, for each type of fiber,
there is a temperature (known as the glass transition temperature). For most acrylic
fibers, the glass transition temperature is in the region of 80-90"C. The majority of
fluorescent brighteners for acrylic fibers are cationic in reaction. Any acrylic fiber
cannot bind a larger number of cationic brightener molecules, than the total number
of the fiber's anionic groups.

Brighteners for Polyacrylonitrile fibers

Basic brighteners are suitable for brightening polyacrylonitrile fibers. The

basicity of the brightener can be attained through either external amino groups or
heterocyclic rings of basic character.

Multi-fiber brightening

Ideally, a laundry detergent should brighten all washable fibers; no such

formulation has been achieved practically. The diaminostilbene dissulfonate
brighteners show about 80% exhaustion on cotton; they have no affinity for cellulose
acetate. Viscose rayon and wash 'n' wear cotton usually show lowered affinity for
these brighteners. While nylon presents no problems, polyester even in cotton
blends-is still a challenge; so are acrylic and spandex fibers, with polypropylene still
to make its appearance. The development of a brightener for anyone of these fibers
is a formidable task. The development of a single brightener suitable for all fibers is
highly improbable because optimum conditions for brightening one fiber will not
necessarily be satisfactory for another fiber.

Paper Brightener

Most papers are brightened by addition of brightener both to the pulp and to
the surface coatings. The exact proportion varied with the type and quality of the
paper. Besides satisfactory exhaust at low temperatures, good paper brighteners
also requires good acid and alum stability as well as compatibility with the paper
fillers. Good affinity to the pulp is also needed, because and unabsorbed whitener is
lost in the effluent or white water from the screen.

Fine papers require relatively less brightener in the pulp, as the pulp is of a
better quality. Fine papers, which require a surface treatment with white pigments
and synthetic resin, are brightened by an after-treatment.

Brighteners for plastics

Plastics are brightened in the melt. The brightener must withstand special
conditions; for example, it must have stability to polymerisation catalysts (peroxides);
sublimation fastness; and the highest possible light fastness. The brightening agent
must not migrate to the surface and, by so doing, cause, "blooming". Good plastics
brighteners, which are especially suited to polyvinyl chloride, are such as (bis-
benzoxazolyl) (ethylenes) and (derivatives of 7-amin-3-phenylcoumarin). In addition
to polyvinyl chloride, plastics based on polystryene, polyethylene, polypropylene,
polyacrylates and polymemthacrylates and cellulose acetate are also brightened.

Brighteners for Cosmetic Preparations

 The use of brighteners for cosmetic preparations, such as creams, salves,
lipsticks, etc. has been proposed, but so significant commercial usage has as yet
developed. Naphthotriazolyl stilbene derivatives may be used for this purpose.

Brighteners for Miscellaneous Application

In addition to the textile, detergent and paper industries, optical brighteners

are also used in various other branches of industry. Such as for the brightening of
feathers, fast, gelatine, wood shavings and sawdust, for the brightening of paints,
leather, furs and straw. The photographic industry makes extensive use of optical
brightening agents. They are also added into developers for coloured photographs
where they improve the coloured on the one hand and slow down the fading of
colour photographs on the other. They are added to lubricants to increase their
fluorescence.

Biological aspects

Brighteners have no detrimental effect on bacteria. The recent reports of

Snyder, Neutomm Glashoof and co-workers indicate that brighteners in general use
are not hazardous. Brighteners do not affect the appearance of water, not the taste,
at 1ppm.

# Dr. Himadri Panda

&

# Dr. (Mrs.) Rakhshinda Panda

Devashish Consultants (P) Ltd.,
61, West End City,
Bidholia, Rampur Road,
P.O. Clutterbuckganj - 243502
Bareilly (UP)

e-mail: devashish_1984@yahoo.co.in