DYES

&
PIGMENTS
Course Instructor: Dr. Saima Daud
Department of Chemistry
Abbottabad UST
 Recommended Books

The Chemistry and Dyes and Pigment Dyes and Pigment: New
Applications of Dyes Ahmet Gürses, Metin Açıkyıldız Research

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David R. Waring, Geoffrey Kübra Güneş, M. Sadi Gürses Arnold R. Lang
Hallas
 Recommended Books

Natural Dyes for Textiles: Fundamentals of the Chemistry of

Sources, Chemistry and chemistry and Synthetic Dyes and
Applications application of dyes Pigments
Padma Shree Vankar P Rys H. A Lubs
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 The Chemistry of Colorants
Dyes & Pigments

1. Colorants

2. Difference between Dyes & Pigments

3. History of colorants (Brief)

4. Physical chemistry

5. Classifications

6. Types of dyes and pigments

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 Introduction

– Dyes and pigments are substances that impart color to a material. The term

colorant is often used for both dyes (also called dyestuffs) and pigments.

– The major difference between dyes and pigments is the particle size.

– Dyes are much finer than pigments. Therefore dyes are not UV stable

whereas pigments are usually UV stable.

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 Lightfastness
– Lightfastness properties: The level at which they fade when exposed to light.

– Pigments have the ability to resist this fading process, whereas dyes are more vulnerable to
fading or bleaching caused by ultraviolet light from the sun.

– Sunlight (UV rays) can break electronic bonding of a dye molecule and destroy its color,
which is why dyes fade.

– Most pigments are lightfast, there are also a few pigments called “fugitive pigments”, such
as Rose Madder, that will fade over time.

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 Particle size
– Dye particles are much smaller than pigment particles – imagine the difference between a pinhead (dye) to a

football (pigment).

– As dyes are soluble and pigments insoluble, you might imagine dye particles dissolving in water, while

pigment particles must be suspended in a binder.

– Another difference is bonding properties, so where a dye might chemically attach itself to a substrate on a

molecular level, becoming part of the material, pigments require the binder or carrier to act as a glue of sorts

that is painted on to the substrate and surrounds the pigment and keeping it in place.

– So dyes become part of the material and pigments sit on top in a layer.

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 Difference between Dyes & Pigments

– Dyes after dissolving in liquid are absorbed on the material while pigments make a suspension

with a liquid that bonds with the material surface.

– Dyes are generally soluble in water while pigments are almost insoluble in water.

– Most of the dyes are organic while most of the pigments are inorganic.

– Dyes are available in large number in the market while the number of pigments is very less.

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 Difference between Dyes & Pigments

– Dyes impart color by selective adsorption while pigments adsorb color either by

selective adsorption or by scattering of light.

– Dyes are combustible while pigments are non-combustible.

– Dyes have a short lifetime in comparison to pigments.

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 Dyes and Pigments Acid
red 52

Dyes Pigments
 Dyes are required to solvate  Pigments are specific colorants
during the application process; composed of particles insoluble in the
they often also have some application medium; they are colored,
affinity for the material being colorless, or fluorescent and can
colored. be organic or inorganic, finely
divided solids.
 Selectively absorb light due to  Selectively absorb and/or scatter light
specific chemical nature of dye due to pigment & material

Broadbent AD (2001) Basic principles of textile coloration. Society of Dyers and Colourists, West Yorkshire, England
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 Dyes

– Colorant which is homogeneously dispersed in the dye

medium
– Usually soluble
– Lightfast — resist fading
– Chemically inert
– Good brightening power
– Soluble as possible in order to apply
– Colorfast — resists washing out of fibers
– Naturally occurring or synthetic organics
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 Uses of Dyes

– Coloring fibers and cloth

– Color photography

– Electronics — dye lasers, solar cells, display panels

– Biological and biochemical stains

– Foods and cosmetic

– Lakes pigments used in modern paints

– Ink jet printer inks

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 Historical background of dyes
– In the ancient age usually all the dyes were natural. Some of the natural dyes used in ancient
age were alizarin and indigo.

– Indigo is probably the oldest known dye obtained from the leaves of dyers woad herb Isatis
tinctoria, and the indigo plant Indigofera tinctoria.

– Early dyes were obtained from animal, vegetable or mineral sources, with no to very little
processing.

– The first synthetic dye, mauve, was discovered by William Henry Perkin in 1856. The
discovery of mauveine started a surge in synthetic dyes and inorganic chemistry in general.

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 Historical background of pigments

– Artists invented the first pigments—a combination of soil, animal fat, burnt
charcoal, and chalk—as early as 40,000 years ago, creating a basic palette of
five colors: red, yellow, brown, black, and white.

– In the early age man used earth pigments on cave walls such as yellow earth
(ochre), red earth (ochre) and white chalk.

– Ochres are probably the oldest known pigments, which are colored clays found
as soft deposits within the earth.

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 Sources of Natural Dyes – PLANTS

INDIGO WOAD (poor man’s indigo)

– used since 2000 B.C.
– Member of the mustard
– Extracted from Indigofera family
tinctoria – Common weed in
– “Navy Blue” of English sailors temperate climates
Blue jeans – Leaves contain same
chemical as indigo but in
– Insoluble in water
lower amounts
– Must be chemical reduced to
soluble leucoindigo to use as dye
– Blue robes of priests
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Sources of Natural Dyes – PLANTS

– Alizarin (also known as 1,2-

dihydroxyanthraquinone, Mordant Red
11, and Turkey Red)
– Obtained from roots of Madder —e.g., Rubia
tinctorum
– Root of madder plant found in Europe and Asia
– used throughout history as a prominent red dye,
principally for dyeing textile fabrics.
– Alexander the Great used it to simulate blood.

– Synthetic alizarin was prepared in 1875. 16

Sources of Natural Dyes – BUGS
Tyrian Purple or “Royal Blue”
– Chemically it is 6,6’-dibromoindigo
– 9000 snails produce 1g of dye
– Used primarily before 8th century
A.D. to dye wool and silk
Kermes or rich red
• the most ancient dye in
Europe
 70,000 female oak beetles
produce 1 pound dye
• Cochineal or Deep Red
• Mexico and Central America
• Mexican cactus beetle

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Kermes, Cochineal — Carmine

Chemically similar
structure, light sensitive
Dyed wool and silk —
“carmine red”

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 Reason for the color of a dye
– In 1876, Otto Witt, a German Chemist observed that the color of a dye is due the certain groups containing
multiple bonds known as chromophores.

– As the number of chromophores increases for a dye, the color of the dye also deepens.

– He also observed that not only the chromophores are responsible for the deepening of color but also there
are certain groups which itself does not act as the chromophore but the presence of which deepens the color
of the dye. These groups are known as Auxochromes.

– To explain the origin of color, Valence Bond Theory (VBT) and Molecular Orbital Theory (MOT) are proposed
in modern time.

– The vital difference between the VBT and MOT is that in VBT electrons are treated in pairs while in MOT
electrons are treated singly.
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 Reason for the color of a dye
– Valence bond theory (VBT): According to VBT, in the ground state the electron pairs of a molecule
are in a state of oscillation and absorb a photon of appropriate energy and get excited when placed
in the path of a beam of light. The wavelength of a photon of light adsorbed depends upon the
energy difference between the ground state and the excited state.

– Molecular orbital theory (MOT): According to MOT, whenever a molecule absorbs a photon of
light, one electron is transferred from bonding (nonbonding) orbital to an anti-bonding orbital.
Based on different type of electron present in a molecule, different types of electronic transitions
are possible.

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 Organic dye
– In simple terms, it can be considered that the organic dye molecules contained three main
components such as chromogen, chromophore and auxochrome.

– CHROMOGEN • The chromogen is a chemical compound that is either colored or could be made
colored by the attachment of suitable substituent.

– The chromophore and the auxochrome(s) are also part of the chromogen.

– The chromophore is a chemical group that is responsible for the appearance of color in
compounds (the chromogen) where it is located

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 Color Centers in Organic Dyes
– CHROMOPHORES — “color bearer” structural part of colored molecule
which is responsible for its color

– Conjugated double bond systems

– Aromatic rings

– Azo groups —N=N—

O

– Carbonyl groups —C=O

– Quinoid rings
O 22
AUXOCHROMES
– “color augmenting” groups
– functional group with non-bonded electrons which acts to strengthen or
deepen the color.

—NH2 —OH —OR

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 The Chemical Physics of
Colorants
• Chromophores absorb light within the UV or visible range
• Examples: C=C, C≡C, C=O, C≡N, N=N, NO2
• Different transitions can occur with chromophores
• π → π*, n → π* and n → σ*
• Auxochromes are covalently saturated groups that change the wavelength or
intensity of the absorption maximum
• Examples: NH2, OH, SH, halogens
• Tend to increase wavelngth and intensity through conjugation resonance
• Conjugated chromophores tend to increase wavelength and intensity
• Create an additional set of HOMO/LUMO pairs and increase conjugation area
• Energy difference between HOMO & LUMO is lowered leading to a
bathochromic shift Yadav LDS (2005) Organic spectroscopy. Springer, Dordrecht 25
 The Chemical Physics of Disperse

Colorants
orange 3

• Chromogens are chemical compounds that are colored or could be made colored by Chromophore

the attachment of a suitable substituent (increases the conjugated system size)

• Solvent yellow 7 (4-Hydroxyazobenzene) as an example:
• Colorants possess several important traits Auxochrome
Chromogen
• Absorbs light in the visible spectrum (400-700 nm)
• Have at least one chromophore
• Have a conjugated system
• Exhibit resonance of electroms

Hossain I (2014). Investigation into cotton knit dyeing with reactive dyes to achieve right first time (RFT) shade. Master Thesis. Daffodil International
University, Bangladesh
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 The Chemical Physics of Colorants
• General rules for adjusting color:

• Adding electron-donating groups gives a bathochromic effect.

• Electron-donating and electron-accepting groups in conjugation provide an intense bathochromic effect

• Increasing the number of electron-attracting groups conjugated with electron-donor groups has a
bathochromic effect

• The electron donating group are enhanced by adding alkyl groups to the N-atom

347nm 386nm 443nm 502nm 517nm

Asiri AM (2001) Organometallic dyes: Part 1. Synthesis of orange to cyan dyes based on donor-conjugated-acceptor-chromogenes using ferrocene as the
donor group. Appl Organomet Chem 15:907–915
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 Nomenclature
– The chemical names of dyes are very complicated hence trade names are more popular
instead of their chemical names.
– From the ancient time humans have tried to extract the dyes from plants and other natural
sources to color their clothes and other belongings, such dyes are known as Natural Dyes.
– Indigo and Alizarin are two examples of natural dyes.
– As the natural dyes have very few colors and shades so now a day’s most of the used dyes
are synthetic dyes having several colors and shades.
– Almost all synthetic dyes are aromatic and obtained from coal-tar. Hence synthetic dyes are
also called coal-tar dyes.

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 Color Index (CI) Number
– There is no symmetric nomenclature system worldwide due to which it is usual to have various names

assigned to a single dye by different manufacturers, called commercial names.

– To avoid confusion in it, SDC (Society of Dyers and Colorists) and AATCC (American Association of

Textile Chemist and Colorist) have assigned Color Index (CI) specification in terms of "color index

generic name" and "color index generic number" to a dye, which may have different commercial

names but chemical structure and properties are identical.

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 Color Index (CI) Number
– For example, an acid red dye may have the name, C I Acid Red 1 etc., followed by its C I generic
number as CI 18050 (a five digit number). The C I specification assigned to a dye has been explained in
the following figure.

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 Dyes and Pigments
Colorants

Organic Inorganic
(~15%) (~85%)

Dyes Pigments
Pigments
(75%) (25%)

Chakraborty JN (2010) Colouring materials. In: Chakraborty JN (ed) Fundamentals and practices in colouration of textiles New Delhi. Woodhead
Publishing, India 31
Common Classes of Dyes

According to Chemical According to

Structures Application Methods
• Azo Dyes • Reactive Dyes
• Anthraquinone Dyes • Disperse Dyes
• Indigoid Dyes • Acid Dyes
• Phthalocyanine Dyes • Basic Dyes
• Sulfur Dyes • Direct Dyes
• Nitro and Nitroso • Vat Dyes
Dyes

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