Dyes and Pigments

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What is a dye?
A dye is a coloured compound normally used in solution
which is capable of being fixed to a fabric.
Visible light consists of electromagnetic radiations of wave
length 400-750 nm. Each wave length
associated with a definite energy and produces
a characteristic colour.

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▣ Wave length absorbed colour absorbed complementary colour
▣ 400-435 violet yellow-green
▣ 435-480 blue Yellow
▣ 480-490 blue-green orange
▣ 490-500 green-blue red
▣ 500-560 green purple
▣ 560-580 yellow-green violet
▣ 580-595 yellow blue
▣ 595-605 orange green-blue
▣ 605-750 red blue-green

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▣ Chromophore:-
▣ The colour of organic compound is due to the presence
of certain multiple bonded groups called chromophore.
(Gr. Chroma = colour ; phorein = to bear).

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▣ It has been noted that the presence of chromophore is
not necessarily sufficient for colour. To make
substance coloured, the chromophore has to be
conjugted with an extensive system of alternate single
and double bonds as exists in aromtic rings.

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▣ Auxochromes:-
▣ Certain groups, while not produce colour themselves,
when present along with chromophores in an organic
substance intensify the colour, such colour assisting
groups are called auxochromes. Gr. Auxanein = to
increase chroma.

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▣ For example, azo benzene has red colour, while p-
hydroxyazobenene is brilliant red.

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▣ Similarly, nitrobenzene is a pale yellow substance but
when the auxochrome –OH is present in ortho or para
position, the product become deep yellow.

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▣ The auxochrome –OH deepens the colour by
extending the conjugated system between the
chromophore and the auxochrome due to resonance.

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Classification of Dyes
❖ By Methods of Applications
❖ Type of chromophores present in the structures

By Methods of Applications
(1) Direct Dyes
These can be applied to fabric by direct immersion in water solution
of the dye. A Direct dye contains acidic or basic auxochrome which
combines with the opposite polar groups present in the chemical
structure of the fiber. Wool and silk are readily dyed by this method.

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(2) Disperse Dyes
These dyes are insoluble in water but can be dispersed in a colloidal
form in water. The fabric is immersed in the colloidal dispersion of
the dye. The fine dye particles are absorbed into the crystal structure
of the fabric. Disperse dyes are used with modern synthetic fibers
such as nylon, orlon, polyester and cellulose acetate.
(3) Vat Dyes
Insoluble in water but reduction with sodium hydrosulphite form a
colourless soluble compound which has great affinity for cellulosic
fibers. Indigo is a good example of vat dye.

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(4) Mordant Dyes
This class of dyes have no natural affinity for the fabric. Applied with
the help of salt. These salts are called Mordants (oxides of aluminium
or chromium). Cotton is first treated with mordant then with dye.
Alizarin is an example of a mordant dye. Mordant dyeing is most
suitable for wool and nylon.

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(5) Azoic Dyes:
Suitable for cotton and other
cellulosic fibers

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▣ Reactive Dyes
▣ Reactive dyes are coloured compounds which contain one or two
groups capable of forming covalent bonds between a carbon atom
of the dye and an oxygen, nitrogen or sulfur atom of a hydroxy,
an amino or a mercapto group respectively of the substrate
during dyeing process.

W-D-Q-RG-X
▣ W= Solubilizing group (-SO 3H)
▣ D= Chromogen (colour producing part)
▣ Q= Bridging group
▣ RG= Reactive group
▣ X= Leaving group (Halogens)

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 Classification of Dyes by Structure

▣ 1) Nitro and Nitroso dyes

▣ NO2 and NO groups are chromophores in this class of dyes,
examples are:

▣ Naphthol Yellow 5 Mordant Green 4

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▣ 2) Azo dyes
▣ The azo dyes contain one or more azo groups –N=N- as the
primary chromophore. The common auxochromes are -NH2, -
NR2, -OH, -SO 3H etc. Azo dyes are the most important group of
synthetic dyes. They are highly coloured and can be prepared by
diazotizing an aromatic amine and subsequent coupling with a
suitable aromatic phenol or amine varying substituents a series of
azo dyes can be produced.

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▣ a) Para Red

▣ It was the first azo dye to be prepared, obtained by the reaction of

diazotized p-nitroaniline with β-naphthol.

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▣ b) Methyl Orange
▣ Obtained from Sulphanilic acid by the following steps:

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Mechanism

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▣ Methyl orange imparts orange colour to wool and silk but colour
is not fast to sunlight. It is indicator for acid base titration, it gives
yellow colour in basic solution and red colour in acid solution,
change is due to the structure of ion.

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▣ c) Congo Red
▣ It contains two azo groups, it is a direct dye.

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▣ d) Bismark Brown
▣ It is a brown dye used in Boot polishes, for dye wool and cotton.

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▣ 3) Triaryl methane dyes
▣ In Triaryl methane dyes central carbon is bonded to three
aromatic rings, one of which is in the quinoid form (the
chromophore). The auxochromes are –NH 2, -NR2, and –OH
examples are:
▣ (a) Malachite Green
▣ Malachite Green has deep green-blue colour. Although the colour
fades in light, Malachite Green is used as a Direct dye for wool
and silk.

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▣ (b) Phenolphthalein
▣ It is also a triarylmethane dye but it is better known as an acid-
base indicator

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▣ (c) Anthraquinone Dyes
▣ The para quinoid chromophore is present in these anthracene
type dyes. Alizarin is a typical anthraquinone dye.

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▣ 5) Indigo dye
▣ Indigo is an example of the type of dyes which contain carbonyl
chromophore. It is dark blue crystalline compound insoluble in
water. It is used for dyeing cotton.

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 Synthetic Fibers
▣ Fibers
▣ Fibers were originally of natural origin and were produced from
wool, silk, cotton, flax and similar materials.

▣ Synthetic Fibers: Polyamide, Polyester, Acrylic, Glass fibers

▣ Synthetic Fibers Based on Natural Organic Polymers

▣ Rayon: Regenerated cellulose
▣ Acetate: Partially acetylated cellulose derivative
▣ Triacetate: Fully acetylated cellulose derivative

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▣ Synthetic Fibers Based on Synthetic Organic Polymers
▣ Acrylic: Polyacrylonitrile
▣ Nylon: Aliphatic Polyamides
▣ Polyester: Polyester of an aromatic dicarboxylic acid and a dihydric
alcohol

▣ Synthetic Fibers Based on Inorganic Substances

▣ Glass, metallic, ceramic

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▣ Polyamide: Nylon 6,6 was the first all synthetic fibers made
commercially. The product resulting from the polymerization
reaction of adipic acid and hexamethylene diamine is called nylon
6,6 because each of the raw material chains contain six carbon
atoms.

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 HO2C(CH2)4CO2H + H 2N(CH 2)6NH2
▣ Adipic acid Hexamethylene diamine

▣ 1,6-hexanedioic acid 1,6-hexanediamine

HO2C(CH2)4CONH(CH2)6NH2 + H 2O
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▣ HO2C(CH2)4CONH(CH2)6NHCO(CH2)4CO2H + H2O

HO2C(CH2)4CO[NH(CH2)6NHCO(CH2)4CO]nNH(CH2)6NH + (2n-1)H 2O

▣ Formation of Nylon by stepwise polycondensation

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▣ Polyester: Polyester is an hydrophobic fiber, the rate of dye
diffusion is very low. High temperature (130 ºC) dyeing
conditions provided with pH range 4.5 to 6.00. Polyester fibers
are strong, easy to dry and stable to processing conditions.
▣ The common polyester fibers are polymers of the ester formed
from dimethyl terephthalate and ethylene glycol.
▣ Intermediates: Dimethyl terephthalate is prepared by
oxidation of p-xylene and subsequent esterification wih methyl
alcohol.

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▣ Polymerization and Fiber Production:
Polymerization is a two step process in which the monomer is
first prepared either by an ester interchange between dimethyl
terephthalate and ethylene glycol or by direct esterfication of
terephthalic acid.
▣ p-H3COOCC6H4COOCH3 + 2CH2OH.CH 2OH
▣ p-HOCH2CH2OOCC6H4COOCH2CH2OH + 2CH 3OH
▣ Ester monomer

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▣ p-HOOCC6H4COOH + 2CH 2OH.CH 2OH
▣ 1,4-benzene dicarboxylic acid 1,2-ethanediol
▣ terephthalic acid
▣ p-HOCH2CH2OOCC6H4COOCH2CH2OH + 2H 2O
▣ Ester monomer
▣ The second stage is the polymerization of the monomer.

▣ n (monomer ester) 200 ºC (n-1) HOCH 2CH2OH +

▣ H-[OCH2CH2OOCC6H4CO]n-OCH2CH2OH

Polyethyleneterephthalate

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