TYPES OF DYES

(METHODS OF PREPARATIONS,
CHARACTERISTICS AND USES)

Introduction:
A dye is a coloured compound, normally used in solution, which is capable of being fixed to a fabric.
The dye must be ‘fast’ or chemically stable so that the colour will not wash out with soap and water,
fade on exposure to sunlight, etc. dyeing is normally done in a special solution containing dyes and
particular chemical material.

After dyeing, dye molecules have an uncut chemical bond with the fibre molecules the temperature
and time controlling are two key factors in dyeing. The dyes were obtained from animal, vegetable,
or mineral origin with no or very little processing. By far the greatest source of dyes has been from
the plant kingdom, notable roots, berries, bark, leaves, and wood. Only a few have ever been used
on a commercial scale.

Synthetic dyes are produced from various chemicals. The great majority of dyes are obtained in this
way because of their superior cost, optical properties, and resilience. Both dyes and pigments are
coloured, because they absorb only some wavelengths of visible light. Dyes are usually soluble in
some solvent, whereas pigments are insoluble. Some dyes can be rendered insoluble with the
addition of salt to produce a lake pigment.

Some dyestuffs, such as indigo and lichens, will impart good colour when used alone; these are
called direct dyes or substantive dyes. The majority of plant dyes require a mordant to fix the colour
on fabric; these are called adjective dyes.

HISTORY OF DYE:
Textile dyeing dates back to neolithic period. Throughout history, people have dyed their textiles
using common, locally available materials. Scarce dyestuffs that produced brilliant and permanent
colours such as invertebrate dyes Tyrian purple and crimson kermes were highly prized luxury items
in the ancient and medieval period.

Plant based dyes such as woad, indigo, saffron, and madder were important trade goods in the
economies of Asia and Europe. Across Asia and Africa, patterned fabrics were produced using resist
dyeing techniques to control the absorption of colour in piece-dyed cloth. Dyes from the new world
such as cochineal and logwood were brought to Europe by the Spanish treasure fleets, and they
dyestuffs of Europe were carried by colonists in America.

Yed flax fibres have been found in the republic of Georgia in prehistoric cave dated to 36000 BP.
Archaeological evidences show that, particularly in India and Phoenicia, dyeing has been widely
carried out for every 5000 years. Early dyes were obtained from animal vegetable, or mineral
sources, with no to very little processing. By far the greatest source of dyes has been form the plant
kingdom notably roots, berries, bark, leaves, and wood only a few are used on a commercial scale.

Ancient hieroglyphs describe the extraction and application of natural dyes. Countless attempts have
been made to extract dyes from brightly coloured plants and flowers, yet only a dozen or so natural
dyes are not highly stable and occur as components of complex mixtures, the successful separation
of which would be unlikely by the crude methods employed in ancient times. Nevertheless, studies
of these dyes in the 1800s provide a base for the development of synthetic dyes, which dominated
the market by 1900

The first synthetic dye mauve, was discovered serendipitously by William henry Perkin in 1856. The
discovery of mauveine started a surge in synthetic dyes and in organic chemistry in general. Other
aniline dyes followed, such as fuchsine, safranine, and induline. Many thousands of synthetic dyes
have since been prepared. The discovery of mauve also led to developments within immunology and
chemotherapy. In 1891, Paul Ehrlich discovered that certain cells or organisms took up certain dyes
selectively. He then reasoned that a sufficiently large dose could be injected to kill pathogenic
microorganisms if the dye did not affect other cells. Erlich went on to use a compound to target
syphilis, the first time a chemical was used in order to selectively kill a bacterium in the body, he also
used methylene blue to target the plasmodium responsible for malaria.

PRINCIPLES OF COLOUR:
Dyes possess colour because they:

1)absorb light in the visible spectrum (400-700nm)

2)have at least one chromophore (colour bearing group)

3)have a conjugated system, a structure with alternating double and single bonds

4)exhibit resonance of electrons which is a stabilizing force in organic compounds

When any one of these features is lacking from the molecular structure is lost. In addition to
chromophores, most dyes also contain groups known as auxochromes (colour helpers) examples of
which are carboxylic acid, sulfonic acid, amino, and hydroxyl groups. While these are not responsible
for colour, their Prescence can shift their colour of colourant and they are most often used to
influence dye solubility.

Regarding the requirement of a chromophore generating colour in organic compounds, it is

important to note that the chromophore must be a part of a conjugated system. Placement of an azo
group between methyl groups produces a colourless compound, while a yellow-orange colour
compound is obtained when the azo group is placed between aromatic rings.

Having an extended conjugated system causes a significant bathochromic shift to a darker colour. In
addition to influencing solubility, auxochromes are essential ring substituents in providing target
colours.

Effects of substituent groups within an azo-dye system

1) Adding groups of increasing electron-donating ability to the azobenzene structure has a

bathochromic effect.
2) Electron-donating (NH2) and electron-accepting (NO2) groups placed in conjugation provide
a bathochromic effect. In this regard, nitro groups are especially beneficial, contributing to
their prevalence in disperse dye structures.
3) Increasing the number of electron-attracting groups conjugated with the electron-donor has
a bathochromic effect.
4) The electron-donating effects of an amino group are enhanced by adding alkyl groups to the
N-atom.

THE MAJOR DIFFERENCES BETWEEN DYES AND PIGMENTS:

Dyes:

1) Solubility: soluble in many liquids

2) Number: available in large number

3) Light fastness: lower dyes are much vulnerable. Lights destroyed coloured objects by
breaking open electronic bonding within the molecule.

4) Product resistance: lower as compared to pigments.

5) Size: dye molecules are comparatively smaller

6) Bonding: dye molecules have more electrostatic charges that serve as a method for getting
attached.

7) Imparting colours: dyes can impart colour by selective absorption of the dyes

8) Combustible properties: combustible

9) Chemical composition: organic compounds

10) Longevity: do not last as long as pigments

Pigments:

1) Solubility: insoluble in water and most of the solvents

2) Number: comparatively less in number

3) Light fastness: traditionally pigments have been found to be more light fast than dyes

4) Product resistance: very high

5) Size: pigment particles are about 1-2 microns size, can only be seen under a microscope

6) Bonding: pigment requires the help of a binding for gluing as it is an inert particle.

7) Imparting colours: pigments impart colours by either scattering of light or by selective

absorption

8) Combustible properties: non-combustible

9) Chemical composition: normally inorganic compounds, often involving heavy toxic metals

10) Longevity: last longer than dyes

Natural and synthetic dyes:
Natural dyes are simply dyed substances extracted from natural sources. Although the main source
of dyes for early times, they have largely been replaced by synthetic dyes, which are usually more
reliable, cheaper and can be supplied more readily. Natural dyes still in use include haematoxylin,
carmine orcein.

Colouring materials have been used for many thousands of years by man. Leather, cloth, food,
pottery and housing have all been modified in this way. Some of our most common dyes are still
derived from natural sources. These are termed natural dyes. The colour index used this as a
classification and naming system.

Each dye is named according to the pattern:

NATURAL+ BASE COLOUR+ NUMBER.

Natural dyes are often negatively charged. Positively charged natural dyes do exist but are not in
common. In the other words, the coloured part of the molecule is usually the anion. Although
molecular charge is often shown on a specific atom in a structural formula it is the whole molecule
that is charged. Many, but by no means at all, natural dyes are required for the use of a mordant.

Synthetic dye:

dyes derived form an organic or inorganic are known as synthetic dyes, examples of this class of dyes
are, direct, acid, basic, reactive, mordant, metal complex, vat, sulphur, disperse dye, etc. synthetic
dyes quickly replaced the traditional natural dyes.

They cost less, they offered a vast range of new colours, and they are imparted better properties, to
the dyed materials dyes are now classified according to how they are used in the dyeing process.

CLASSIFICATION OF SYNTHETIC DYES:

Synthetic dyes are classified based on their chemical composition, the type of fibres to which they
can be applied, hue or the method of application. Organic centric days are classified into non-ionic
anionic and cationic, depending on the general structure. Each fibre reacts differently to dyes. Fibre
modification would also react differently to the same dye.

Within a dye classification different hues will have different colour fastness. The Society of dyers are
colourists (SDC) and American Association of textile chemist and colours (AATCC) classified dial based
on their chemical composition. Acid dye, basic dye, reactive dye, direct dye, sulphur dye, disperse
dye, are the different categorizations of synthetic dyes.

ACID DYE:

Acid dyes are water soluble anionic dyes, containing one or more sulfonic acid substituents or other
acidic groups. An example of the class is acid yellow 36.

Acid dyes are applied to fibres such as silk, wool, nylon, and modified acrylic fibres using neutral acid
dye baths. Acid dyes are not substantive to cellulosic fibres. Most synthetic food colours fall in this
category. The dyeing process is reversible and may be described as follows:

Basic or cationic dye:

This group was the first of the synthetic dyes to be taken out of coal-tar derivatives. As textile dyes,
they have been largely replaced by later developments. They are still used in discharge printing, and
for preparing leather, paper wood, and straw. More recently they have been successfully used with
some readymade fibres, especially the acrylics.

Basic dyes were originally used to colour silk, wool, linen, hemp, etc. without the use of a mordant,
or using agent. With a mordant like tannic acid, they were used on cotton and rayon. Basic dyes give
brilliant colours with exceptional fastness to acrylic fibres. They can be used on basic dyeable variants
of nylon and polyester.

Basic brown 1 is an example of a cationic dye that is readily protonated under the pH2 to 5
conditions of dyeing.

DIRECT DYE:

These are the dyes which can be applied directly to the fabrics from an aqueous solution. These are
most useful for fabrics which can form hydrogen bonds with the dyeing of fabrics. The direct dyes
mainly the basic dyes and were widely hailed because they made it unnecessary to use a mordant or
binder in dyeing cotton.

The colours are not as brilliant as those in basic dyes but they have better fastness to light and
washing, and such fastness can be measurably improved by after treatments (diazotized and
developed). Direct dyes can be used on cotton, linen, rayon, wool, silk, and nylon. These dyes usually
have azo linkage -N=N- and high molecular weight. They are water soluble because of sulphonic acid
groups.

Direct orange 26 is a typical direct dye.

AZOIC DYE:

Azo dyes contain at least one azo group (-N=N-) attached to one another or often two aromatic rings.
Those dyes are used primarily for bright red shades in dyeing and printing since most other classes of
fast dyes are lacking good red dyes.

Azoic dyes, called naphthols in the industry, are actually manufactured in the fabric by applying one
half of the dye. The other half is then put on and they combine to form the finished colour. Unless
they are actually applied and well washed, they have poor fastness to rubbing or crocking.

The production of bluish red Azoic dye from the following two components is an example.

NITRO DYE:

Nitro dyes are polynitro derivatives of phenols containing at least one nitro group ortho or para to
the hydroxyl group. It Is used to dye wool. It consists of two or more aromatic rings (benzene,
naphthalene).

Example: Martius yellow

DISPERSE DYE:

These dyes were originally developed for dyeing secondary cellulose acetate fibres. These dyes are
relatively insoluble in water and are prepared for dyeing by being ground into relatively fine powder
in the Prescence of dispersing agents. In the dye bath, a suspension of the dye particle dispersion
produces a very dilute solution of the dyes, which are absorbed by the fibres. This dye class is used to
dye polyester, nylon, acetate and triacetate fibres.

Disperse yellow 3, Disperse red 4, and disperse blue 27 are good examples of disperse dyes.

VAT DYE:

The vat dyes are insoluble complex polycyclic molecules based on the quinone structure (ketoforms).
The term vat comes from the old indigo method dyeing in a vat: indigo had to be reduced to light
form. Vat dyes are made from indigo, anthraquinone and carbazole.

They are successfully used on cotton, linen, rayon wool, silk and sometimes nylon. Vat dyes are also
used in the continuous piece of dyeing process sometimes called the pigment application process.
The dyeing produced in this way have high wash and light fastness.

An example of vat dye is vat blue 4 (indanthrene).

MORDANT DYE:

These dyeing of fabrics do not dye the fabric directly but require a binding agent known as mordant.
The mordant acts as a binding act between the fibre and dye. Some dyes combine with metal salts
(mordanting) to form insoluble coloured complexes (lakes). These materials are usually used for the
dyeing of cotton, wool or other protein fibre. The metallic precipitate formed in the fibre producing
very fast colours highly resistant to both light and washing.

Example: mordant red 11

REACTIVE DYE:

These dyes react with the cellulosic fibre to form a covalent bond. This produces dyed fibre with
extremely high wash fastness properties. These are the dyeing of fabrics which contain a reactive
group which combines directly with the hydroxyl or the amino group of the fibre. Because of the
chemical reaction the colour is fast and has a very long life. Cotton, wool or silk can be dyed with this
type of dyeing fabrics.

Example: this type is the reactive blue 5 dye.

SOLVENT DYE:
These dyes are water-insoluble but soluble in alcohols, chlorinated hydrocarbons, or liquid ammonia.
These colours are applied by dissolving in the target, which is invariably a lipid or non-polar solvent.
The colour index uses this as a classification and naming system. Each dye is named according to the
pattern: - solvent + base colour + number. They are used for colouring synthetics, plastics, gasoline,
oils and waxes.

Example: solvent yellow 32

SULPHUR DYE:

The sulphur dyes provide very deep shades, which have excellent resistance to washing but poor
resistance to sunlight. They will dye cotton, linen and rayon but not brightly. A problem with sulphur
dyes especially the back colours is that they make the fabric tender, or weaken its structure, so that it
breaks easily. Sulphur dyes are applied to cotton from an alkaline reducing bath with sodium
sulphide as the as the reducing agent. They are low cost and have good fastness to light, washing and
acids.

Example: Sulphur red 7

Properties of dyes:
These dyes are economic dyes are generally used to produce dark shades such as dark greens, dark
blues and blacks.

These dyes have good levelling and colour fastness properties.

The interaction between fibre and dye is established through very strong ionic bonds, which are
formed between the anionic groups of the colourant and ammonium cations on the fibre. Chromium
or the meatal ion acts as a bridge between the dye and fibre, which gives rise to a very strong
linkage, resulting into excellent fastness properties.

Examples of a few dyes which are widely used in the industries in the dyeing of textile materials
described below:

JACK FRUITS (Artocarpus heterophyllus lam)

It’s a very popular fruit of south India, and other parts of India. The wood of the tree is cut into small
chips and crushed into dust powder and then subsequently boiled in water to extract the dye. After
mordanting treatment of dyed fabrics, yellow to brown shades are obtained. The cotton and jute
fabrics are dyed by this dye. It belongs to the family of moraceae. The dye consists of morin as a
colouring molecule.

TURMERIC (curcuma longa)

The dye is obtained from the root of the plant. The turmeric root is dried, crushed in powder form
and boiled with water to extract the dye. It can be used in the dyeing of cotton, wool and silk. Proper
mordanting treatment improves colour fastness to wash.

The brilliant yellow shade is obtained after dyeing with turmeric natural dye. Turmeric is a rich source
of phenolic compounds known as curcuminoids. The colouring ingredients in turmeric are called
curcumin. Curcumin is diarylheptanoid existing in keto-enol form. Turmeric is a member of curcuma
botanical group.

ONION (allium cepa)

The papery skin of onion is the main source of the dye. Onion skin is boiled to extract the colour and
subsequently can be dyed with or without mordanting the fabric. The resulting colour is from orange
to brown. It contains pigments called pelargonidin (5,5,4,7 tetrahydroxy antocyanidol). The amount
of colouring pigment present varies from 2.0 to 2.25 %.

HINA (lawsonia inermis L)

It is the leaf of the plant that is traditionally used in making colour designs on the hands of women.
The leaf of the plant is dried, crushed and subsequently coiled with water to extract they dye form
the leaf. The mordanted fabric gives colour from brown to mustard yellow. This is the dispersed dye
type colour. Hence, polyester and nylon can be dyed by Hina.

However, it stains wool and silk giving it a light brown colour. Hina is commonly known as lawsone.
The chief constituent of Hina leaves is hennotanic acid. It is a red orange pigment. Chemically
hennotanic acid is 2-hydroxyl-1,4 naphthoquinone. The colouring molecules have strong
substantivity for protein fibre.

INDIGO (Indigofera tinctoria)

It is the seed of the plant. The full matured plant has 0.4% colour on weight of the plant. The plants
are steeped in water until the fermentation start. When the hydrolysis of glucoside is completed, the
liquor is separated from the plant debris. The extract is aerated which converts indoxyl to indigotin
which separates out as a precipitate.

The shade of natural indigo is difficult to reproduce exactly. The variety of blue shade on cotton can
be obtained by the application of natural indigo. It is kind of vat dye and hence need reductive
vatting with liquid jaggery and citric acid dithionate.

The precursor to indigo is indican which is colourless water-soluble compound. Indican hydrolyses in
water and releases B-D glucose indoxyl. The oxidation of indoxyl resulted in indigotin. The average
yield of indican from an indigo plant is 0.2-0.8%. indigo is also present in molluscs.

The molluscs contain mixture of indigo and 6,6’-dibromo indigo (red), which together produce a
colour known as Tyrian purple. During dyeing due to air exposure, dibromo indigo is converted into
indigo blue, and the mixture produces royal blue colour.
MADDER OR MAJINSTHIA OR RUBIA (Rubia tinctorum)

The dye is obtained from the root of the plant. The root is scrubbed, dried in sunlight and finally
boiled in the water to extract the dye in solution. The dye has red colour. The cotton, silk and wool
fibre can be dyed with madder at a temperature of 100 degree Celsius for time period of 60 min, and
subsequently dye solution is cooled. Bright red shade is produced on wool and silk and red violet
colour on cotton.

This is mordantable type of acid dye having phenolic (-OH) groups. The colouring matter in madder is
alizarin of the anthraquinone group. The root of the plant contains several polyphenolic compounds,
which are 1,3-dihydroxyanthraquinone, 1,4- dihydroxyanthraquinone, 1,2,4-trihydroxyanthraquinone
and 1,2- dihydroxyanthraquinone.

TEA WASTE (Camellia sinensis)

India is one of the biggest consumers of tea. The left-over waste is collectable in large quantity. The
extract of tea waste can be used as a natural dye in combination with different mordants, which can
produce yellowish brown to brown shade.

This is a mordantable dye. Flavonoids, flavanols, and phenolic acids are the main colouring
components in waste of the tea. Polyphenols, which are mostly flavanols, are known as catechins
with epicatechin and its derivatives.

SAFFLOWER (Carthamus tinctorius)

The safflower petals are soaked in distilled water and subsequently boiled with water for more than
2 hours, and its repeated two times. The solution is filtered and the filtrate is vacuum dried. The
obtained powder is having strength of 20-30%. In dyeing it produces cherry red to yellowish red
shade. Safflower contains natural pigment called cardamine.

The biosynthesis of cardamine takes place by chalcone (2,4,6,4-tetrahydroxy chalcone) with two
glucose molecules and that resulted in the formation of safflower A and safflower B.

SAPPAN WOOD (Caesalpinia sappan)

Aqueous extraction is used to extract the dye from sappan wood. Alkali extraction can also be used.
It produces bright red colour. It produces an orange colour in combination with turmeric and maroon
shade with catechu. The sappan wood tree is found in India, Malaysia and the Philippines. The
colouring pigment is similar to logwood. The same dye is also present in Brazil wood.