Lec-15

fluorescent whitening agents (FWA), also called optical brighteners (OB), designed to
brighten colors or mask yellowing in plastics, lacquers, paints, inks, photo processing
solutions and fibers. These optical brighteners work via a fluorescent mechanism which
absorbs light in the UV spectrum and emits light in the blue region of the visible
spectrum to yield a brighter, fresher appearance. It also known as

• Fluorescent whitening agent

• Fluorescent brightening agent
• Physical bleaching agent
• Brightener

Day light or sunlight has a yellow tint. Cotton also has a yellow tint even after
bleaching. There is a yellow colored pigment in human eyes. These overall reduce
the whiteness. Blue is the complementary color of yellow which balance whiteness. A
surface containing OBA emit more light than the total amount of daylight falling on
it, giving an intense brilliant white as it absorbs short wave length (Ultra violet) & re-
emit it into a longer wave length (violet to blue) thus increase blue in reflected light.
The effect is only operative when incident light or rays contain significant proportion
of ultraviolet radiation.

Reasons for naming physical bleaching agents:

In normal bleaching (chemical bleaching) we use oxidizing or reducing agents(e.g.H2O2,

NaOCl, etc). These agents destroy the natural and added coloring matters in the
fibres. Thus they give a white effect. It involves chemical reactions, either oxidation
or reduction. So they are chemical bleaching agents. On the other hand, optical
brightening agents introduce color complementary to that of the natural coloring
matters. The result obtained is, the distribution of reflected light becomes more
uniform through out the spectral range and the surface becomes apparently white. It
involves no chemical reaction as bleaching process. So it is called physical bleaching
agent.

Suggested Applications:

• Molded thermoplastics
• Films and sheets
• Clear and pigmented lacquers
• Paints
• Printing inks
• Synthetic leather
• Ultraviolet tracer
• Photo processing solutions
• Adhesives
• Fibers
Whitening of Textile materials:

The whitening/improving whiteness of natural and man-made textile materials can

be done in 3 ways-

1. By chemical bleaching: In chemical bleaching, the color of the impurities is

destroyed nearly completely by using oxidizing or reducing agents. For bleached
cotton, the curve is not uniform (i.e. reflectance is not uniform throughout the
central range). The reflectance is different in violet- blue and yellow-red region.

(3) MgO
100
(4) OBA treatment
80
(2) bleached cotton

(1) Blueing
60
Reflectance (%)

0
40
00
20

400 500 700

Wave length (nm)

Fig: showing whitening effects of different treatment

2. b. By physical bleaching (adding some blue coloring matter): Physical bleaching

involves the introduction of a complementary color whereby the undesirable
color is made invisible to the eye in an optical manner. By the operation of
Blueing, the yellow rays from the incident light are absorbed and therefore the
reflected light becomes deficient in the yellow rays. The residual yellow
impurities present in the fabric absorb some blue rays from the incident light.
This leads to the absorption of yellow and blue rays to almost the same
extent. Thus the white effect is produced by a substractive process, in which
the amount of incident light absorbed by the fabric increases and the reflected
light which is now deficient in both components almost to the same extent,
produces a white effect. Though the treated product appears whiter to the
eyes it is actually grayer than the untreated material.
3. By applying OBA: By this method we add a complementary color of yellow
red region which is done by OBA capable of absorbing the light of shorter
wavelength (UV region) and fluoresce (or remit) the light of higher wavelength
(visible region). This add extra light in reflectance & balance the yellow &
blue portion of light which increase total reflectance.
Ideal White:

An ideal white body has a reflectance of 100%, that means it reflects all incident
light falling on it. In other words, ideal white is a white which reflects 100% of the
incident light at al wavelengths.

A block of MgO provides a near perfect white surface and the whiteness of other
surface is compared with that of the MgO block. BaSO4 is another substance which
is very near to a perfect white body. This means the reflectance of MgO and BaSO4
is very close to 100% and their spectral energy factor, β = 1 (Approx.). But in practical
sense a perfect ideal white body is impossible.

120 (1) Ideal white

100 (2) MgO

(3) OBA treatment
80
(4) bleached
+blueing
60
Reflectance (%)

0
40
00
20

400 500 600 700

Wave length (nm)

Fig: Ideal white and other bodies reflectance curve

Mechanism of OBA:

Nearly 80% of all OBAs produced are derived from stilbene derivatives, the latter
absorbency in the ultra violet regions at (λ) = 342 nm. All the OBAs are dyestuffs,
but in place of the chromophoric system which is the characteristic for dyes, it
contains a fluorescing system, and like a normal dye certain substituent which
promote the affinity depending on the type of fiber on which it is applied.
Fluorescence is produced by the absorption of radiation having a high energy on
the part of the molecule, which re – emits this radiation of lower energy i.e. of
longer wave length, the difference in energy being transformed in to kinetic energy.
To enable a molecule to fulfill this function, it must be built according to certain
structure principles.

FWA + UV (340nm) FWA*

FWA* FWA +hv(450nm) + heat

Most of the brightener will hardly fluoresce in powder form; their fluorescence will
only appear in solution. There are some types, which will not fluorescence in
solution and will only show this property after they have been applied on the fiber.
Thus, it can be concluded that fluorescence is not only depends on the structure
of the molecule, but also on its condition. Whether a fluorescent substance is
suitable as brightener can only be determined after it has been applied to the
textile fiber. Apart from this the product must meet certain demands in respect of
properties such as fastness to washing and light, etc
DESIRED PROPERTIES OF FLUROSCENT WHITENING AGENTS FOR TEXTILES USE

An optical brightener must have two following properties:

• It should be optically colorless on the substrate

• It should not absorb in the visible part of the spectrum

Beside these, it should have the following properties:

• It should have a conjugated system of single and double bonds

• Its molecule should be planner
• It should contain electron-releasing groups such as –OH, NH2 etc.
• It should be sufficiently stable to light
• It should be non-toxic
• When exposed to white sunlight for long time it must not decompose to give
any colored products.
• It should have good solubility, should not have its own color and good
substantivity for the textile substrate under OBA application
• It should have good leveling and penetrating properties
• It should be compatible and stable with finishing chemicals, auxiliary and
process such as heat and temperature
• It should be stable and fast to the common oxidative and reductive
bleaching chemicals and bleaching systems.

Application categories of Optical Brighteners:

Textile fluorescent brighteners can be divided into three application categories:

• Anionic whiteners containing solubilizing sulfonate groups are used for cotton,
wool, and polyamides. These are applied to cellulosics by exhaust method or
padding at a pH of 8-11 or higher. These products are powder and available
with very high affinity, good light and wash fastness and stability to peroxide
and bleaches.
• Cationic whiteners are used mostly for acrylic fibers. These are applied by
exhaust method at 95°C and a formic acid catalyst. These are usually pyrozoline
and heterocyclic based chemicals.
• Nonionic whiteners are used mostly for polyester, acetate, acrylic and
polyamide fibers. These are applied with carriers to polyester using exhaustion
at boiling temperature. Thermosol and pad-dry-bake procedures are also
applicable.

Application process of OBA:

OBA is mostly applied on cotton materials. Treatment of cotton with OBA is usually
carried out with some other finishing processes. But OBA treatment is not a
substitution of scouring-bleaching. OBA cab be applied by-

• Exhaust method
 • Padding method

Which is fixed by subsequent heat treatment.

Exhaust method:

Exhaust method is mainly used for loose stock, yarns, garments or its parts, woven
fabrics and knitgoods which give poor or unsatisfactory results in padding processes.
At first goods are entered at room temperature, then 0.05 -0.6% OBA is added to
the liquor along with electrolytes (if required).

Then temperature of liquor is raised to 100°C and continued for 30 mins. A typical
recipe of OBA treatment along with bleaching is as below:

Detergent : 0.5-1 g/l

Wetting agent : 0.5 g/l

Caustic soda : 1.5 g/l

H2O2 (50%) : 5 g/l

OBA : 0.5% (owf)

Time and temp : 100°C for 30 mins

After treatment : Hot wash at 80°C for 10 mins, soaping at 80°C for 10
mins, again hot wash at 70°C for 10 mins

Padding method:

Padding method is a continuous method of OBA treatment. Woven fabrics or knitgoods

are passed in an unfolded and open-width state through a small trough filled with
OBA and salt (if required) and subsequently squeezed with squeeze roller to control
the liquor pick-up. During the drying or heat treatment (if required), the fluorescent
whitener is fixed on the substrate. OBAs used in padding procedures must have low
substantivity during the padding operation. This is an important prerequisite for level
whitening with no tailing.
The effectiveness of fluorescent brighteners is dependent on several factors:

1. Nature of textile goods

2. Temperature

3. Addition of salt

4. Liquor ratio

5. Concentration of fluorescent brightener

6. pH of bath

7. Time