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TEXTILE

DYES

By
Mansoor Iqbal
M.Sc (Applied Chemistry)
Senior Research Associate, Textile
PCSIR Laboratories complex Karachi
Ministry of Science & Technology
Government of Pakistan.

REHBAR PUBLISHERS KARACHI


COPY RIGHT

Cover story: Original specimen of Mauvein, the first organic dye ever synthesized, made
by W.Perkin in 1856.Some yarn colored by this dye and ALIZARINE, another important
dye.courtesy of M.Holford of material in the science museum, London.
Dedicated to my
Father (Late)
Mr. Nabi Hussain
FOREWORDS

It is indeed a matter of much pleasure to write the forewords of the book


written by my student Mr.Mansoor Iqbal.I always please my student in
writing such monographs. I do also understand, writing a technical book is a
difficult task.Mr.Mansoor has performed an outstanding example, which
definably follow up and continuation.
Looking at the topics and contents of the book it was much needed book for
industry and academia, Textile industry needs such books to upgrade the
skills and knowledge of the people involved in processing, teaching and
research and development activities.
I am sure this book will fulfill the reader’s to their highest degree of
satisfaction. However improvements are always possible. I must request the
readers to indicate the improvements and suggestion to the author so that he
can incorporates the same in the later edition.

(Dr.Syed Ishrat Ali)


Professor & Chairman
Dept of Applied Chemistry & Chemical Technology
University of Karachi

April 26, 2008


PREFACE
Textile industry is the backbone of our country economy. During last few
years a wide net of the professional textile institutes both in private and
Government sector have been established that shows the present demand and
interest of our peoples in this field. The textile books available in our country
are very rare and beyond the scope of our student both from purchasing and
understanding point of view. Textile dyes is the first attempt of its kind ever
published in Pakistan. Dyes are coloured organic compounds, which impart
colour to the fabric. Most important classes of dyes for textile application are
discussed in a simple and easy style. Discussions are lead from fundamental
concepts to the fastness properties evaluations of dyes. Interactions of dye
molecule with different fiber polymer system have also been discussed. A
chapter Banned Amines also included, which will helpful to understand the
modern ecological issues of dyestuffs and textile industry. The book will be a
handy and reliable source of information for textile students, teachers of
textile chemistry, sales executives in dyes, dye house laboratories, dyeing
department of textile mills, research workers and many others. Reference
departments in the libraries will find this volume an essential addition to their
offerings. Suggestions are welcome for the improvement in book in next
edition. I offer my warm welcome to book lovers, please feel free to contact
me to share knowledge, literature and books regarding textile.

MANSOOR IQBAL
Senior Research Associate, Textile
E-mail: mansoorprocessing @ hotmail.com
Cell: 0344 - 3046460

March 25, 2008


CONTENTS

Chapter # 1 DYES & COLOUR (1-6)


Dyes and colour
Modern theory of colour
Otto Witt theory of colour
Valence bond approach to colour
Bathochromic effect

Chapter # 2 HISTORY OF DYESTUFFS (7-21)

Chapter # 3 CLASSIFICATION OF DYES (22-46)


Classification of Dyes
Classification according to chemical structure
Nitro Dye
Azo Dyes
Aniline Yellow
Butter Yellow
Chrysoidine
Methyl Orange
Orange II
Para Red
Resorcin Yellow
Disperse Red 1
Congo Red
Diphenlymethane Dyes
Auramine O
Triphenylmethane Dyes
Malachite Green
Pararosaniline
Rosaniline
Crystal Violet
Xanthene Dyes
Fluorescene
Eosin
Rhodamine B
Phthaeleins
Phenolphthalein
Indigoid and Thioindigoid Dyes
Preparation of Indigo
Structure of Indigo
Tyrian Purple
Thioindigo
Anthraquinoid Dyes
Alizarin
Structure of Alizarin
Classification according to method of application
Direct Dyes
Mordant Dyes
Vat Dyes
Ingrain Deys
Disperse Dyes
Chapter # 4 DYES AND FIBRE POLYMER SYSTEM (47-62)
Wool Fibres
Silk Fibres
Cellulosic Fibres
Monoazso Dyes
Dyes with Mixed Chromophores
Cellulose Acetate Fibres
Cellulose Triacetate Fibres
Poyamide Fibres
Polyester Fibres
Polypropylene Fibres
Polyurethane Fibres
Polyacrylonitrile Fibres
How do dyes stick to fibres?

Chapter # 5 REACTIVE DYES (63-86)


Nucleophilic substitution systems
Vinylsulphone dyes
Evidence for chemical combination
Commercial popular reactive dyes
Cold Dyeing Brands
Hot dyeing brands
Bifunctional Dyes (Sumitomo Chemicals Japan)
Reactive dyes in pakistan
Sumitomo chemicals (Osaka, Japan)
Kyung-in synthetic corporation
Reaffix dyestuffs Korea
P.T.Sinar (Indonesia)
Meghmani dyes & intermediates India
Jay chemicals India
Dyestar (Germany)
Sunfix Chemdyes Corporation
Everzol dyes (Taiwan)
Clarient dyes Switzerland

Chapter # 6 DIRECT DYES (87-91)


Direct dyes
Chemical constitution of direct dyes
Classification according to dyeing behavior
Class A
Class B
Class C

Chapter # 7 DISPERSE DYES (92-100)


Azo Dyes
Anthraquinone Disperse Dyes
Miscellaneous Disperse Dyes
Methine or Styryl Dyes
Quinphthalone dyes
Coumarin Dyes
Chapter # 8 VAT DYES (101-109)
Indigoid Dyes
Thioindigoid Dyes
Anthraquinone Vat Dyes
Chapter # 9 SULPHUR DYES (110-116)
Sulphurised Vat Dyes
Ready-reduced and Solubilised Sulphur Dyes
Recent Developments
Examples of Important Commercial Sulphur Dyes
Chapter # 10 ACID (ANIONIC) DYES (117-123)
Acid or anionic dyes
Acid dyes can be divided into four groups
Dyeing Process
Dyeing of Nylon Carpets
Application of Acid Dyes to Silk
Dyeing of Modified Acrylic and Polypropylene

Chapter # 11 BASIC (CATIONIC) DYES(124-126)


Basic or cationic dyes
Dyeing of Acrylic Fibres
Chapter # 12 BANNED AMINES (127-142)
What are banned amines?
What is Eco-Labeling of Textiles?
Name the agencies, which have accredited Textiles
Committee Laboratories?
what are the advantages of testing of textiles in an
accredited laboratory?
State the list of dyes banned by Government?
Ecomark criteria for textiles
Product specific requirement
Jute and jute products
Silk and silk products
Pesticide registered for use on cotton
Coupled Amines released from Azo-dyes
Chapter # 13 FASTNESS PROPERTIES OF DYES (143-166)
Colour fastness
Acids and Alkalies
Evaluation and Classification
Colourfastness to Bleaching with Chlorine
Evaluation and Classification
Colourfastness to Bleaching with Peroxide
Carbonizing (AATCC 11-1975)
Crocking (AATCC 8-1974/116-1974)
Degumming (AATCC 7-1975)
Dry cleaning (AATCC 132-1976)
Fulling (AATCC 2-1975)
Dry Heat (Excluding hot Pressing)
Hot Pressing (AATCC 133-1976)
Light fastness
Lightfastness (General Method) (AATCC 16-1974)
Lightfastness-Carbon Arc (AATCC –16-A-1974)
Sunlight-Fastness (AATCC 16B-1974)
Daylight Fastness (AATCC 16C-1974)
Lightfastness Carbon Arc Alternate Light Darkness
(16D-1974)
Lightfastness-Xenon Lamp-Continuous Light
Lightfastness-Xenon Lamp-Alternate Light-Darkness
(AATCC 16F-1974)
Carbon-Arc Lamp (Fade-Ometer)
Exposure Cabinet
Black-Panel Thermometer
Lightfastness Standards
Xenon-Arc Lamp
Alternate Wash-and-Light (AATCC 83-1974)
Phototropism (AATCC 139-1975)
Ozone in the Atmosphere Under Low Humidity
Wash fastness
Prespiration (AATCC 15-1976)
Steam Pleating (AATCC 131-1974)
Stoving (AATCC 9-1975)
Water Spotting (AATCC 104-19756)
Dispersibility of Disperse Dyes
Dyestuff Migration (AATCC 140-1976)
Dyes & Colour
1
Any coloured compound is not a Dye or Dyestuff. A dye is a
coloured organic compound that absorbs light strongly in the visible
region and can firmly attach to the fiber by virtue of chemical and
physical bonding between group of the dye and group on the fiber. To be
of commercial importance a dye should be fast to light, rubbing and
water.
Colour and dye have always played an important role in the life of
man from time immemorial. Preparation of a colour and dyeing of cloth
date back to antiquity. Fabrics dyed in indigo were found in the tombs of
predyanstic Egypt. Let us now try to understand how we get sensation of
colour.

Modern theory of colour:


Colour is a physiological sensation associated with the wavelength
of light striking the retina of the eye. The sensation of colour is produced
when light having a wavelength within the visible region of
electromagnetic spectrum strikes the retina of the eye.
The visible region of the spectrum extends from 4000 to 7500 Å in
wavelength.

4000 4500 5000 5500 6000 7000


Ultra Violet Blue Green Yellow Orange Red Infra
Viole red
High Increasing Energy Low

When white light falls on a substance, the light may be completely


reflected and in this case substance will appear white. If it is completely
absorbed, the substance will appear black. If a substance absorbs all
visible light except that corresponding to e.g. yellow, it will transmit or
reflect only yellow colour and will be seen as yellow. However, it is
1
generally seen that, light of only one colour is absorbed in which case the
substance will appear to have the complementary colour. Thus, if the
light is absorbed from the violet region of spectrum, the substance will
be seen as yellow. If light is absorbed from the red region, the substance
will appear green.

Wavelength Colour absorbed Visible colour


absorbed (Å) (complementary
colour)
4000 – 4350 Violet Yellow Green
4350 – 4800 Blue Yellow
4800 – 4900 Green blue Orange
4900 – 5000 Blue green Red
5000 –5600 Green Purple
5600 – 5800 Yellow green Violet
5800 – 5950 Yellow Blue
5950 – 6050 Orange Green blue
6050 – 7500 Red Blue green

Otto Witt theory of colour (1876):


An early theory of dyes first formulated by O. Witt provided a
basis for understanding the reaction between colour and structure of the
molecule. According to the O. Witt colour theory a dye is made up of
two essential kinds of parts, Chromophores and Auxochromes. He
designated a group that produces colour as a chromophore (Gr, Kuroma.
colour + Phors carrier). Chromophores are unsaturated groups. Presence
of at least one such group is essential to produce a colour in an organic
compound and a molecule containing such a group is called as
chromogen.
Some most effective chromophores are
0 0
0
+
0
-N=N-
-N=0 N
Azo
0
O O
Nitroso P-Quinad O-Quinad
Thus for example nitrobenzene is pale yellow, azobenzene is orange-red,
p-quinones are yellow and o-quinones are orange or red.
2
Certain other unsaturated groups produce colour only when several of
them are present in a molecule and when they are conjugated. They are

Thus though acetone is colourless, biacetyl colour.

C=C C=O C=N-

Ethylene Carbonyl Azomethine

O
||
CH3 – C – CH3 Acetone Colourless
O O
|| ||
CH3 – C – C – CH3 Biacetyl Yellow
O O
|| ||
CH3 – C – CH3 – C – CH3 Acetonyl Colourless
Acetone

O. Witt also observed that certain groups, while not producing


colour themselves, are able to intensify the colour when present in a
molecule together with a chromophore. These are called auxochromes
(Gr, auxanein = to increase). The most effective auxochromes

H
|
–OH –OR –NH2 –N–R –NR2
Hydroxyl Alkoxy Amino Alkylated
Amines

Thus nitrophenols and nitroanilines are more intensely coloured


than nitrobenzene and aniline and are deep yellow to orange.
Further auxchoromes are salt forming groups, i.e., they are basic
or acidic and makes the coloured compound to attach itself to the fabric,
so that it is fast to light, soap and water. Acidic auxochromes like – OH,
--COOH and – SO2H give acidic dyes and basic auxochromes like – NH2
3
– NHR and – NR2 gives basic dyes. Auxochromes like – SO3H group has
little value as auxochrome but it has a solublishing effect. The halogen
atom also functions as auxochrome and the relative order of colour
intensifying effect is I>Br>Cl. It can be observed that all the
auxochromic groups contain atoms with unshared pair of electrons.
According to Witt theory of colour and constitution chromogen is
a compound which contains a chromophore –N=N. It is a bright red
compound but not a dye.
C6H5 – N = N – C6H5
On the other hand p-hydroxy-azo benzene is acid dye because
H2O – C6H4 – N = N – C6H5
It contains – OH group, an acid, auxochrome, and p-amino azobenzene is
a basic dye, as it has basic auxochrome – NH2.
Azobenzene, anthraquinone, dinitro benzene are chromogens
O O
|| ||
and are coloured due to the presence of –N=N, --C--C, --NO2, groups
respectively. The chloromogens, on reduction give the colourless
compounds, for examples azobenzene, a bright red compound, on
reduction forms the colourless hydrazobenzene.

H2
C6H5 – N = N – C6H5 C6H5 – NH – NH –C6H5
Azobenzene Hydrazobenzene

Sometimes the conversion is reversible. In this case the reduction


products are called “Lecuo compounds”.
H2
Azobenzene Red Hydrazobenzene (colourless)
Oxidation

H2
Indigo Blue Indigo white (colourless)
Oxidation

Sometimes reduction completely decomposes the coloured


compound, such reduction products are called “Leuco compounds”.
4
Valence bond approach to colour:
Like many other theories, the Witt theory has also been replaced
by modern electronic theory. According to this theory, it is the resonance
stabilization of excited states that is responsible for the absorption in the
visible region. When ultraviolet or visible light is absorbed by a
molecule, an electron is excited, that is, it is promoted to an orbital of
higher energy. The wavelength of light absorbed depends on the energy
difference between the excited and ground states of the molecule. The
smaller difference between the two states, the longer is the wavelength of
the light absorbed.
The energy required to promote an electron depends upon the
environment of the electron. Sigma (σ) bond electrons are firmly held
and very high energy (or short wavelength) is necessary to promote
electrons and may at times break the molecule and form free radical.
Pi (π) electrons are less firmly held and require less energy (or
longer wavelength) to excite. Electrons belonging to conjugated systems
required even less energy (still longer length). Conjugation and
resonance stabilize the excited state by sharing and delocalizing higher
energy of the excited electron. As conjugation and resonance increases,
the wavelength of light absorbed also increases and when the wavelength
is long enough to be in the visible region, we observe colour. This can be
explained with the help of following example.
Ethylene absorbs light in the ultraviolet part of the spectrum 1800
Å. Butadiene, with two conjugated double bonds, absorbs at 8170 Å (a
wavelength closer to visible region) and hexatriene, with three
conjugated double bonds, absorbs at 2580 Å (a wavelength still closer to
visible region). But all the three compounds are colourless. However, as
the number of conjugated double bonds increases, the absorption falls in
the visible region, for example in β-carotene there are eleven conjugated
double bonds and absorbs at 4510 Å, that is, in the visible region. The
light absorbed is blue and we see the complementary orange colour.
H2C + CH2
CH2 = CH – CH = CH – CH = CH2 CH2=CH–CH = CH2
Ethylene 1: 3 Butadiene
(Colourless) 1: 3: 5 Hexantriene
(Colourless) (Colourless)

5
H3 C H3 H3 C H3
H3 H3 H3 H3
C C
H2 C CCH=CHC=CHCH=CHC=CHCH=CHCH=CCH=CHCH=CCH=CHC H2

H2 C H
3 H3 CC H2
H2 H2
Β-CAROTENE
Benzene absorbs light at 2550 Å and is colourless. Aniline, which
absorbs light at about 3000 Å, is also colourless; nitrobenzene absorbing
light slightly above 4000 Å is pale yellow and p-nitro aniline absorbing
light at 4500 Å is a yellow compound.

Bathochromic effect:
In this case benzene ring may be considered to be chromophore,
while amino group and nitro group auxochromes. When they are
conjugated, the longer resonance system decreases the energy gap
between the ground state and excited state transitions, thus producing
visible colour. All these groups, which lengthen wavelength of
absorption, are bathochrome groups. Thus displacements (or shift) to
longer wavelength are known as bathochromic effects or bathochromic
shift and displacements to shorter wavelength are hypsochromic.
Hypsochromes are groups which decrease resonance. This is done by
forcing the pi (π) orbitals out of planarity. For example when alkayl
group on benzene ring is ortho to adjacent rings or chains, the molecule
is distorted out of planarity and resonance is decreased. As the number of
fused rings increases, the absorption in the visible region also increases
e.g. naphthacene absorbs in blue region and is yellow. Pentacene absorbs
in orange region and is blue. Graphite, which is a sheet of benzene rings
is black, it absorbs all colours almost completely.

6
History of Dyestuff 2
The historical development of the synthetic dyestuffs dates back to
1856, when eighteen year old, W.H. Perkin discovered the synthesis of
Mauveine, a basic dye, by accident, while he was engaged in the study of
the action of potassium dichromate on aniline sulphate. He successfully
converted the process he had developed in laboratory to a large-scale
production, and demonstrated the application of the dye on silk. The
intermediates nitrobenzene and aniline required in the production were
also made commercially by him. Nitrobenzene was earlier prepared by
Mansfield in 1847.
This historical discovery of the first synthetic dye was followed by
the syntheses of numerous dyestuffs made for the first time in their
laboratories by the individuals or the group of scientists putting in
constant efforts and getting due credit for their discoveries. Earlier
discoveries worth mentioning include the synthesis of Magenta, a basic
dye (Verguin, 1859), Aniline blue, a basic dye (Girard and de Laire,
1860), Aurine, a basic dye (Runge and then Kolbe and Schmitt, 1861),
Methyl Violet, a basic dye (Bardy, 1866), Induline, a basic dye (Dale and
Caro, 1863), Bismark Brown, an azo dye (Martius, 1863), Aniline Black,
an ingrain dye (Light foot, 1963) Alizarin, an anthraquinone dye (Graebe
and Libermann, 1868), Fluorescein, a basic dye (Bayer, 1871), Eosin, a
basic dye (Caro, 1871) Orange II and Orange IV, azo dyes, (Roussin,
1876,) Methylene Blue, a basic dye (Caro, 1876), Malachite Green, a
basic dye (O’Fischer, 1877), Indigo, an indigoid vat dye (Bayer, 1880),
Para red, an azo dye (Read, Holiday and Sons, 1880), Crystal Violet, a
basic dye (Kern, 1883), Auramine, a basic dye (Kern, 1883), Congo Red,
an azo dye (Boettiger, 1884), Tartrazine, an azo dye (Ziegler, 1884),
Indigo, an indigoid vat dye by newer syntheses (Heumann, 1890 and
Sandmeyer, 1899), Indanthrene blue, a vat dye (Bohn, 1901), Benzo fast
scarlet 4 BS, an azo dye (Israel and Kolthe, 1900), Indanthrene Dark
Blue BO, Green B, and Black BB, vat dyes (Bally and Isler, 1904),
Indanthrene Golden Orange G, a vat dye (Scholl, 1905), Indanthrene
7
Brown GR, olive R and Khaki GG, vat dyes (MLB, 1908 to 1911),
Indanthrene violet RN, Red BN and Red Violet RRN, vat dyes (Ullmann
and coworkers, 1909 and 1910), Hydron Blue R, a sulphurised vat dye
(Hass, 1908), Naphtol AS, a coupling component for azoics (Grieshei-
Elektron,1912), Alizarin Direct Blue A, an anthraquinone dye (Herzberg
1913) and Brilliant take colours from basic dyes (BASF, 1913) and
Brilliant lake colours from basic dyes (BASF, 1913). All these
discoveries required requisite intermediates for the production as large-
scale ventures and the technology for the production of the intermediates
suitable for the dyes was naturally made available. These discoveries
were made before the First World War (1914 to 1918) and until about
1920, as the effect of the war, the progress of chemical industry became
stagnent.
All the discoveries made during the period mentioned above (1856
– 1914) came into picture as a result of certain other auxiliary discoveries
made and certain important theoretical suggestions initiated by pioneers
of organic chemistry. There is a likelihood that as an error, the invaluable
work of many individuals and organizations might not have been
recorded Griess discovered diazotisation in 1858 and the coupling of
diazonium salts subsequently in 1864 and his work is so valuable even
today, that based on his discoveries, the azo dyes were developed and
today they cover partically half the quantum of the total quantity of
dyestuffs under commercial use. All the chemists, including the colour
chemists are also indebted to the grand services rendered by Kekule in
the field of organic chemistry by suggesting his institutional benzene and
allied aromatic hydrocarbons. A large number of organic reactions were
investigated by various scientists during the period and nitration,
sulphonation, oxidation, reduction, alkylation, quaternization, alkali
fusion, thionation etc., were developed probably without the sufficient
background of the knowledge of organic chemistry since the exact nature
of an the action of variety of reagents was not well established. The study
of the correlation of colour and chemical nature of the compounds had
been attempted which no doubt helped many other scientists to choose
the right tracks. The discoveries of the organic compounds like
Bnaphthol H-acid J-acid, Primuline Base, various anthraquinone
derivatives, etc., worked as intermediates and led to the discoveries of
then novel dyestuffs which are popular even today.
8
During the First World War, Neolan colours (metal complex dyes)
were discovered by the Society of Chemical Industry at Basle (1915).
An important dyestuff intermediate phthalic anhydride was also
discovered by air oxidation of naphthalene using vanadium pentoxide as
catalhyst by Gibbs in 1917.
After the first world war, the major discoveries made were in the
anthraquinonoid vat dyes such as caledon Jade Green (Davas and
cowlorkers, 1920), Golden yellow GK (Kranzlein and coworkers 1922),
Indanthrene Navy Blue R (Wilke, 1931), etc. Thje azoic colours made by
the combination of diazonium salts from fast bases and coupling
components naphtols, picked up market since 1921 to early 1930s as a
result of the discoveries of other members of naphtol AS series and
naphtol ASG as well as a number of fast bases. Indigosols, which are the
soluble vat colours, and Cyanine dyes which are useful sensitisers for
photography and dyeing and printing were developed by the German
industry. With the discovery of man-made fibre cellulose acetate,
obtained by acetylation of the hydroxyl group present in natural fibre
(cotton), newer dyestuffs were searched and Ionamines (Green and
Saunders, 1922) and S.R.A. colours (Baddiley and Shepherdson, 1923)
making use of aqueous dispersons of the insoluble colours for dyeing of
cellulose acetate were developed. Light fast Chlorantine colours for
cotton with the use of Cynuric chloride intermediate were developed by
Ciba in 1924. ICI in 1934 developed a process of manufacture of copper
phthalocyanine as Monostral Fast Blue BS, which was actually observed
in 1928 by Dandridge as a surprise, during the manufacture of
phthalimide in an iron pan. The corresponding water-soluble dyes were
also marketed by ICI in 1947 and by IG which were sulphonated copper
phthalocyanines. The chlorination of copper phthalocyanine afforded
green pigment.

The Second World War, which broke out in 1939 once again,
disturbed the progress of the dyestuff industry. Until 1945, whatever
discoveries made during the World War II, were kept in dark or
unpublished. It was only after 1945, except German industries, the
dyestuff industries, in other developed countries started taking shape
with revival of interest in earlier discoveries. Many new organizations
came up and started establishing their products in the world market, for
9
which a lot of efforts were made to introduce newer products for
colouration of textile fibres. With the result, a great number of new
members in already established classes of dyes such as direct cotton
dyes, acid dyes, vat dyes, etc. were introduced. Newer series of dyes for
cellulose acetates fibre were also discovered. Pigment emulsion
techniques for printing of textile materials were developed. Optical
brighteners for whitening of textile fibres were introduced in the market
in 1940.
The first firm, Arlabs, manufacturing dyestuffs and allied products
in India, began in 1940 and various firms made further progress of
manufacturing various intermediates and dyes in India after the
independence.
With the discoveries and exploitation of newer synthetic fibres
such as polyester and polyamide, it became necessary to design new
structures of dyestuffs, which could suit the dyeing of these hydrophobic
fibres. There was a revival of interest to check the suitability of earlier
known dyes for these fibres also, for example, acid dyes were applicable
to the polyamide fibre and the series of metal complex dyes were brought
in the field. The dyestuffs suitable for cellulose acetate were found to be
applicable to polyester. However, they being inferior to this fibre due to
its compact structure, it was necessary to modify the original cellulose
acetate dyes from their fastness and dyeing character point of view.
Various newer techniques were developed in the application of the
dyestuffs on polyester and in one of such developments, the application
of the insoluble dyes in the form of microfine disperions called as
disperse dyes were brought into commercial practice which is being
followed even today.
The first reactive dye, the dye which reacts with the fibre during
dyeing process forming a chemical covalent bond with the fibre structure
as against the conventional dyes which are physically bound to the fibre
structure, was discovered by Rattee and coworkers of ICI in a sensational
way, while examining the dyeing character of certain dyes containing
active chlorine attached to triazine ring, and earlier known to give fast
dyeing especially to washing on cotton. A reactive dye after dyeing by a
suitable method remains attached to the fibre because of chemical
bondage and its washing fastness is of high standard. After a series of
triazinyl class of reactive dyes was introduced by ICI, many dyestuff
10
firms concentrated their research and development investigating novel
systems for the production of reactive dyes. Dyestuffs containing several
groups of reactive systems were patented and few of them were
commercially exploited. Hoechst introduced B-sulphato ethyl sulphone
called as vinyl sulphone reactive dyes, which were superior in their
dyeing properties to triazine class.
The progress was constantly made in the fields of pigments,
fluorescent brighteners, and azo dyes from novel diazonium salts, etc, as
a result of the advancements in the chemistry of heterocyclic compounds.
The introduction of heterocyclic moities in the dyestuff structures
modifies their property in many ways. Smaller heterocyclic systems can
restrict the molecular weight of the dye changing its dyeing character,
certain heterocyclic systems effect the shift of the absorption maximum
of wavelength to higher wavelength in the visible range of spectrum,
generally most of the heterocyclic systems in dyestuff help to increase
the fastness properties such as sublimation fastness in disperse dyes. A
pouring number of patents were filed worldwide on the subject,
exploiting usage of many heterocyclic systems.
With the advances in newer analytical techniques such as visible,
ultra violet and infrared spectra, it became possible to detect the
properties of dyes. Newer tools in modern organic chemistry such as
Nuclear Magnetic Resonance and Mass Spectra surpassed all the
conventional methods of elucidating the structure of complex organic
molecules. Chromatographic methods helped to separate various
dyestuffs from their isomers, etc. These techniques and the overall
growth of the technology and chemical engineering sciences made it
possible for the colour chemists to broaden their ideas and grow fast.
With the advent in the polymer chemistry, newer polymers such as
plastic materials and fibres were put into the market. Polypropylene and
polyacrylic fibres are important discoveries for a colour chemist.
Polypropylene finds industrial and restricted domestic applications.
Polyacrylic commonly known as PAN Polyacrylonitrile fibre has
partially replaced wool because of the matching of its properties with
other synthetic fibres especially polyester required for obtaining the
blends. The dyestuffs were synthesised by examining the properties and
characteristic groupings or side chains is quite adament to known dyes
for the synthetic hydrophobic fibre polhyester, and therefore, special
11
dyes had to be searched. Cationic dyes which are similar to basic dyes
(both the classes carry a +ve charge on the main structure of the dye,)
were soon developed for polyacrylic fibre. It was suggested to modify
both these newer synthetic fibres by addition of certain metal additives
during their manufacture so as to increase the sites for dye attachments
on the fibres. Modacrylates came in the market, which were copolymers
of acrylonitrile and similar monome5rs having side chains present in the
other monomers after copolymerisation provided better sites for dye
attachment to the fibre. Astrazon class of dyes earlier developed were
found to be the most suitable for dyeing of polyacrylic fibres and
constitute even today an important class of cationic dyes. The optical
brighteners initially synthesised for brightening cotton, wool, etc. were
extended by suitably modifying the structures to brighten polyamide,
polyester, etc.
In the recent years a rapid growth of all the classes of dyestuffs is
being made, the technology is being innovated, short-cuts are being
followed, the basic raw materials are being newly examined and novel
intermediates are being searched in more systematic manner. The colour
and chemical constitution study based on the modern concepts has
helped to strike the right targets of researches in the field. It is, however,
possible to find several gaps and combinations of isolated facts in the
further addition to known types of dyes. Some of the discoveries made
recently were based on the logical thinking in appropriate direction based
on certain published or exploited facts elsewhere. For example, the
combination of disperses dyes and reactive dyes, suitable for polyamide
and they are better than acid dyes or disperse dyes in their dyeing
properties. The insertion reactions of the azides and carbenes in organic
chemistry are applied by introducing azido group in the dyestuff
molecule and applying them on polyester by insertion technique as a
reactive dye for polyester which of course has not been commercialised
as yet. Fluorescent dyestuffs could be said to be a bridge joining
fluorescent brighteners and dyestuffs.
Our country, in the present days has become almost self-sufficient
in the production of dyestuffs, though certain items are still being
imported. The earlier trend of importing many intermediates as well as
dyestuffs from developed countries have practically stopped because of
our restricted import policy. This policy was whole heartedly supported
12
by organised sectors as well as small scale industries which took a bold
step in making larger quantity and better quality of variety of products
which are direct requirements for dyestuff industries. The export market
possibilities in the recent years have also increased the horizon of many
ambitious dyestuff firms to enter in the worldwide competition in the
dyestuffs and intermediates.
The main threatening problem in the industrial world facing today
and applicable to dyestuff field is the pollution problem. The dyestuff
industrial waste in the form of atmospheric gases and wastewaters
pollutes the neighbouring area. The handling of hazardous chemicals like
solvents, cyanides, lead salts, mercury salts, etc, which are often required
in the dyestuffs and their intermediates production is posing problems.
The handling and production of carcinogenic intermediates regularly
involved in the production, such as benzidine and its derivatives, a- and
B-napthylamines, diphenylamine, etc., has created setbacks. For the
pollution control, newer techniques have been introduced and are further
being developed by absorbing the Industrial gases and giving appropriate
treatments to waste waters to minimise pollution. An exaustive study has
been made on careful handling of solvents, chyanides, etc. The processes
where lead salts, mercury salts, etc., were essential are abondoned or
replaced by new safer methods. These developments are notable from
ecology point of view. Benzidine and its derivatives are important for the
production of many dyestuffs consumed in huge quantities, however,
because of the carcinogenic nature of these intermediates they are being
banned all over the world and are being replaced by new comparatively
much safer diamines. The use of β-nahthylamine for making its
derivatives is no more in practice, the methods are abondoned or
modified by using a much safer sulphonic acid, Tobias acid (β-
naphthylamine – &-sulphonic acid). Many such examples can be cited in
the dyestuff chemistry.
It is rightly said that the development made in any field has to face
major setbacks. It is hoped that the future development of intermediates
and dyes to be exploited commercially will be thoroughly investigated
first from the point of view of ecology and safety of human beings and
animal as well as plant kingdom.
Ever since primitive people could create, they have been
endeavoring to add color to the world around them. They used natural
13
matter to stain hides, decorate shells and feathers, and paint their story on
the walls of ancient caves. Scientists have been able to date the black,
white, yellow and reddish pigments made from ochre used by primitive
man in cave paintings to over 15,000 BCE. With the development of
fixed settlements and agriculture around 7,000-2,000 BCE man began to
produce and use textiles, and would therefore add color to them as well.
Although scientists have not yet been able to pinpoint an exact time
where adding color to fibers first came into practice, dye analysis on
textile fragments excavated from archaeological sites in Denmark have
placed the use of the blue dye woad along with an as yet unidentified red
dye in the first centuryCE.
In order to understand the art and history of dyeing, we must first
understand the process of dyeing itself. According to Webster’s
dictionary, dyeing is “the process of coloring fibers, yarns or fabrics by
using a liquid containing coloring matter for imparting a particular hue to
a substance.” There are three basic methods of “imparting a particular
hue” to a substance. The first is by staining an item, a temporary means
of coloration where the color is rubbed or soaked into an item without
the benefit of some sort of chemical fixative to preserve the color. The
next is the use of pigmentation, wherein the color is fixed to the surface
of an object by another adhesive medium. A true dye is when the color of
a substance is deposited on another substance in an insoluble form from a
solution containing the colorant.
Natural dyes can be broken down into two categories: substantive
and adjective. Substantive or direct dyes become chemically fixed to the
fiber without the aid of any other chemicals or additives, such as indigo
or certain lichens. Adjective dyes, or mordant dyes, require some sort of
substance, (usually a metal salt) to prevent the color from washing or
light bleaching out. Most natural dyes are adjective dyes, and do require
the application of a mordant (the metal salt) solution to the fibers at some
point in the dyeing process. Aluminum and iron salts were the most
common traditional mordants, with copper, tin and chrome coming into
use much later. In rural areas where these metals were not widely
available, plants were also used as mordants, especially those that have a
natural ability to extract such minerals from the earth, such as club moss.
Most ancient and medieval dyers mordanted their yarns and fabrics
before dyeing them. Alum and Iron were used as mordants in Egypt,
14
India and Assyria from early times, as there are many alum deposits in
the Mediterranean region. Medieval dyers used alum, copper and iron as
mordants, and cream of tartar and common salt were used as to assist in
the dyeing process.
Different fibers also have different tendencies to absorb natural
and synthetic dyes. Protein and cellulose fibers (the two main divisions
for fibers used historically in spinning and dyeing) need to be mordanted
differently because of their structural and chemical composition.
Mordants to cellulose fibers such as cotton and linen usually involve the
use of washing soda or tannins to create an alkaline dyebath. Tannins
(plantstuffs, such as oak galls containing tannic acid) are widely used in
dyeing cellulose fibers as they attach well to the plant fibers, thus
allowing the dyes to attach themselves to the tannins, whereas they might
not be able to adhere to the fibers themselves (Tannins are sometimes
classified as mordants in and of themselves, but are usually considered a
chemical to assist in the dyeing process.) Mordants for protein fibers,
like wool and silk, are usually applied in acidic dyebaths. Alum with the
assistance of cream or tartar is the most common mordant used to assist
the dyes in taking to the fibers.
Since the difference in mordanting different fibers has been
mentioned, it would be remiss not to spend a moment on the historic
nature of the fibers themselves. Wool, a protein-based fiber, has been
found in Europe dating back to 2000 BCE. It was a common medieval
fabric in both dyed and natural colors, and was processed by both
professional manufacturers and housewives. Silk, another protein-based
fiber, was imported from China to Persia as early as 400-600 BCE. It
became quite popular in the Late Middle Ages, and major silk
manufacturing centers were set up in France, Spain and Italy. These silk
production centers also became centers of dye technology, as most silk
was dyed and required the highest quality dyes available. Cotton was
considered a luxury fabric, as it was imported all the way from India and
usually dyed or painted before it was shipped. Cotton was also valued
because of the brightness and colorfastness of the dyes used to color it,
and also for its use in making candlewicks. Samples of cotton fabrics
have been found in India and Pakistan dating to 3000 BCE, but it did not
appear in Europe until the 4th century. Cotton waving establishments
were formed in Italy in the 13th & 14th centuries but they did not make a
15
significant economic impact on the industry as they produced a coarser
quality of fabric than the imported fabric, and therefore had difficulty in
obtaining a good supply of cotton fiber.
Scientists are almost certain that dyeing was practiced throughout
the world, but it is difficult to obtain proof on this for two reasons. First,
not all cultures left written records of their practices. Second, because of
the wide variance of environmental conditions and degree of geological
disturbance, it is not easy to find well-preserved evidence of dyed textiles
in many archaeological sites. A Chinese text from 3,000 BCE lists dye
recipes to obtain red, black and yellow on silks. Ancient Indian texts
describe several different yellow dyestuffs, how to obtain reds from the
wood and bark of certain trees, and also notes the use of indigo to create
blues on cotton. In Central and South America they dyed bast fibers
(plant fibers) in shades of red and purple with the bodies of the cochineal
insects (Dactylopius coccus).
A Greek artifact known as the Stockholm Papyrus details
dyestuffs and techniques in almost a recipe fashion as it was practiced
Egypt in the third and fourth centuries CE. The great detail in which the
preparation of the fibers and the dyeing materials and the dyeing process
itself are recorded has led scholars to believe that it had to have been
practiced for thousands of years previously in order to raise the process
to such a science and art. It discusses mordanting the fibers using alum,
copper and iron oxides to darken or “sadden” the red, blue, green and
purple dyes, as well as the occasional use of tin and zinc. It describes
over ten different recipes for using alkanet (Anchusa tinctoria) root as a
dye employing camel and sheep urine, lentils, vinegar, wild cucumber
and barley malt among others as aids to producing color. It also gave
recipes on obtaining purple hues by overdyeing the alkanet with woad
(Isatis tinctoria), madder (Rubia tinctorum), kermes (made from the dried
bodies of the female shield louse or scale insect (Kermes ilicis)) and the
heliotrope plant (Heliotropium arborescens). Excavated coptic textiles
dating from the fourth to the sixth century CE show use of weld (Reseda
luteola) to produce yellow, madder and woad for dark purple, and blue
from indigo (Indigofera tinctoria). Scientists have been able to date a red
obtained from Egyptian madder root from the fourteenth century BCE.
In the Mediterranean before the advent of Christianity, a whole dyeing
industry arose around Tyrian purple. Tyrian purple is produced from the
16
mucous gland adjacent to the respiratory cavity within some species of
Purpura and Murex species of shellfish. The shells were crushed to
extract this fluid, which only turns purple once it has been applied to the
fiber and exposed to light and oxidation with the air. The Phoenicians,
skillful shipbuilders and sailors that they were, scoured the coastlines for
sight of these whelk shells, and established a dyeworks and trading
station wherever they found a plentiful population of these shellfish.
Coastal Indians of Mexico were also using shellfish, but their delicate
method involved blowing and tickling the shellfish to get them to spit out
the dye precursor directly onto the cotton fibers. Even Ireland can
produce archaeological evidence of dyeing with the native dog-whelk
shells in the seventh century CE. Both Discorides, the Greek physician
and Pliny the Elder, the Roman naturalist, mention in their first century
works the preparation and dyeing of wool with various shellfish to
produce colors of red, blue, purple and violet after first being mordanted
with soapwort (Saponaria officinalis), oxgall or alum. (Schetky, 4) Both
authors also mention the use of Indigo from the Orient to obtain blues,
and Herodotus describes its use in a 450 BCE text. Dioscorides also
mentions other dye plants of the ancient world, including madder, saffron
(Crocus sativus) and weld for yellow, and woad for blue. Walnut shells
(Juglans nigra), oak bark (Quercus sp.), pomegranate flowers (Punica
granatum) and broom (Genista tinctoria) were also used in conjunction
with various mordants; but galls formed on trees could mordant
themselves, being high in tannic acid.
In Europe the art of dyeing rose to new heights with the diversity
of climate, culture and migration/invasion waves. This was further
influenced by the direct impact of trade instigated by the Crusades and
furthered by the growing cultural awareness of the Renaissance period -
everyone in Europe wanted the exotic, colorful dyestuffs from the Orient,
and later from the Americas. Caravans of camels would cross the Gobi
desert for centuries bringing goods from China to the Mediterranean. By
the 12th century the two main trade routes for imported dyestuffs headed
through Damascus: the first led from Baghdad to Damascus to Jerusalem
and Cairo, the other went to Damascus to Mosul to the Black Sea to
Byzantium (Istanbul).
Venice was one of the major early centers for imported dyestuffs,
supplying Brazilwood (Caesalpinia sappan) from the East, lac (another
17
insect dye) and indigo from India from the fifteenth century CE onward.
Dyers of Italy soon became adept in their use; in 1429 the Venetian
dyer’s guild wrote a book for its members containing a number of
different dye recipes, including Brazilwood and lac. The Plictho de Larti
de Tentori by Venetian author Giovanni Ventur Rosetti (sp - also listed
as Giovanventura Rosetti) in the 1540s lists instructions for using both
lac and indigo, as well as 217 other recipes for dyeing cloth, linen, cotton
and silk with many varieties of dyestuffs. It would remain the best source
for dyeing instruction for the next 200 years.
From Venice the dyestuffs were traded by ship around the coast of
France to Flanders, Southampton and London; in the Mediterranean at
Florence, Pisa and Genoa; and northward on the continent to the
distribution centers of Basle and Frankfurt (Schetky, 6). Basle was a
noted center of trade for saffron, the expensive yellow obtained from
certain species of crocus. In later years crocus were grown in that area
directly, and the crop became such a vital part of the local economy that
they crocus was featured on the city’s coat of arms. Frankfurt housed
trade fairs from the twelfth to fourteenth centuries that dominated the
trade of many dyestuffs, but mainly that of locally grown woad, the only
blue dyestuff available to European dyers before the coming of indigo.
Many regions in Germany specialized in growing and processing the
woad through its complex fermentation process, and strict legislation was
placed on every aspect of the trade.
The government of Spain controlled the trade of cochineal, the red
dye from the bodies of the Cochineal bugs of Central America. In 1587
approximately 65 tons were shipped to Spain, and from there northward
throughout Europe. Italian dyers shunned cochineal in favor of the
already established dye kermes, made from the dried bodies of the
female shield louse or scale insect (Kermes ilicis) (Schetky, 4). It’s use
was first recorded in 1727 BCE and it was long the standard red dye for
silk, wool and leather, but the intense colorific value and relative
cheapness of cochineal soon eliminated most of the kermes use in
England, so Spain hung on to control of their lucrative monopoly.
European dyers reached their height of skill in the thirteenth
century, mainly due to the guild systems who vigilantly maintained a
high standard of quality. In many countries dyers were graded by the
guild system, the master dyers being allowed to use the major “fast” dyes
18
while their lesser colleagues were restricted to the slower, “fugitive”
dyes. In some places it was forbidden to possess, let alone use, major
dyestuffs unless you were a member of a guild. In Germany, the dyers
and woad workers were regulated by the guilds, each grower having to
present his crop to a “sworn dyer” to determine its quality, weight and
condition before it could be sold. (Grierson, 8-9) English producers of
woad had fewer restrictions, mainly that of a proclamation in 1587 to
restrict growers to certain field size and ensure that no woad mills were
sited within three miles of a royal residence, market town or city because
of the highly offensive odor they emit. Even the local doctors in Venice
in 1413 city fathers to prohibit dyeing with either woad or ox-blood after
March first because of the “unhealthy smell.” France had developed an
extensive and efficient textile industry by the 13th century and also
increased the dyers craft by developing varied techniques to achieve
additional colors from the basic dyestuffs. At the end of the 16th century,
there were over 220 master dyers listed in Paris alone.
While the powerful guild system had numerous dyestuffs with
which to blend their color palates of fiber for the bluebloods and wealthy
merchants, dyeing in the lower classes was a bit more restrictive.
Without the money (or connetions) to buy indigo, cochineal and
turmeric, clothing in the country tended to natural colors – whites,
blacks, browns, grays, and tans of the natural colors of the fibers
themselves, with the reds, greens and yellows of local plants used for
both food, medicine and dyes. In short, home dyers used any plants they
could lay their hands on that would give a good color. Some colors were
even derived accidentally. Washing beehives in preparation for making
mead could yield yellows and golds. Blackberries and Bilberries that
stained the fingers of pickers could also be used to achieve pale blues
and purples, although these were not often color or lightfast. In England,
the multitudinous variety of lichens and mosses produced greens, grays
and browns.
By the seventeenth century a worldwide shipping and trading
network was in place, allowing dyestuffs from all parts of the world to be
brought to Europe. Legislation from earlier centuries to protect the
growers and users of specific dyestuffs was overturned in favor of new
demands and standards set by the growing consumer-focused society
who wanted more colors and better quality. In the eighteenth and
19
nineteenth centuries the practice of colonialism insured that there would
always be a supply of foreign dyestuffs, and the Industrial Revolution
met the demands of large-scale productions while finding new ways to
make the colors brighter and longer-lasting to wear and washing.
As textile weaving technology advanced with the advent of
machines to spin, design and weave fabric, dyers were forced to be able
to produce dyes with exact shades, matching color lots and most
importantly, ones that would stand “fast” to the new mechanical and
chemical processing. In addition, exporters wanted colors that would
stand up to tropical sunlight and still be exotic enough for foreign tastes.
Dyers in turn demanded from their supplier’s purer chemicals and
dyestuffs of consistent quality. Hand in hand, dyers, manufacturers,
chemists, and dyestuff producers worked hand in hand to keep up with
the progress of technology. Chemists in many countries had found a
means of extracting highly concentrated powders or pastes from
traditional dyestuffs that made stronger colors, such as cochineal carmine
and madder garancine. Other procedures were used to extract indigo that
gave us sulphonated indigo and Saxon blue. A few novel dyes
(precursors of future chemical dyes) such as the yellow obtained from
picric acid also made an appearance. With the tremendous rise in the
interest of Chemistry in the mid nineteenth century, several important
innovations in dyeing came about. W.H. Perkin, a student of celebrated
European scientist Wilhelm von Hoffman, accidentally discovered the
first synthetic dye in an attempt to synthesize quinine. The 18-year old
student’s purple precipitate, later called mauviene, was quickly put into
industrial application, allowing the young Perkin to start his own factory
in London to commercially produce his dyestuff. Two years letter a
synthetic red dye called magenta or fuchsine was patented in France, and
hardly a year passed until the end of the century without a new synthetic
dye being patented.
Eventually, the old natural dyes lost popularity in favor of the
newer synthetic ones. By the end of the nineteenth century a few Scottish
tweed producers were the only ones still using natural dyes, and now the
use of natural dyes on a commercial scale barely exists, mainly in remote
areas where people have either little access to synthetic dyes or a vested
interest in retaining their ancient dyeing customs. Use of natural dyes is
gaining popularity again with the renaissance in hand crafting, most
20
notably in the fields of spinning and weaving, basketry, papermaking and
leather craft. There is also renewed scientific and historic interest in
natural dyeing, both to help identify dyestuffs in recently discovered
archaeological finds and to preserve the dyed textiles housed in museums
and private collections.
As Su Grierson says in her book Dyeing and Dyestuffs, “Whilst
the dyeing industry of today keeps pace with modern science, the future
use of natural dyes will also follow a new path, but one firmly.

21
Classification of Dyes 3
Dyes may be classified in two ways. The organic chemist
classifies them according to a common parent structure (Chemical
Classification). The dyer, who is only interested in fixing the dye to the
fibre, classifies them according to the method of application.

CLASSIFICATION ACCORDING TO CHEMICAL


STRUCTURE

(1) Nitro Dyes:


Nitro dyes are polynitro derivatives of phenols containing at least
one nitro group ortho or para to the hydroxyl group. They are of
relatively little importance industrially, because the colours are not very
fast. Examples of this class are picric acid (2,4,6-trinitrophenol), Maritus
yellow (2, 4-dinitro-1-naphthol), and Naphthol yellow S (2,4-dinitro-1-
naphthol-7-sulphonic acid).

OH OH
OH
O2N HO3S
NO2 NO2 NO2

NO2
NO2 NO2
PICRIC ACID MARITUS YELLOW NAPHTHOL YELLOW S

Naphthol yellow S can be used to dye wool, and is one of the


colours permitted in foods.

(2) Azo Dyes:


The azo dyes represent the largest and the most important group of
dyes. They are characterised by the presence of one or more azo groups
(–N=N–), which form bridges between two or more aromatic rings.
Preparation of azo dyes involves the following two steps.
22
Step 1. Conversion of primary aromatic amines into diazonium
compounds by treatment with sodium nitrite in excess hydrochloric acid
(Diazotisation).

NH2 + HNO2 + HCl + -


N2Cl + 2H2 O

A PRIMARY A DIAZONIUM
AROMATIC AMINE COMPOUND

Step2. Coupling of diazonium compounds with phenols,


naphthols, or other aromatic amines. Coupling with phenols and
naphthols is carried out in basic solution; coupling with amines is carried
in acid solution.
OH(-NH2,-NR2)
OH(-NH2,
+ -
N Cl + H
2
-HCl -NR2)
N=N
A DIAZONIUM A PHENOL, A DYE
COMPOUND NAPHTHOL or
AMINE

The above reactions are carried out at low temperatures (0 – 5o)


because diazonium compounds are usually unstable. In the resulting
dyes an aromatic system joined to the azo group is the chromophore, and
the hydroxyl group or amino group is an auxchrome.

To simplify the description of azo dyes, only the coupling step


will be shown. It will be assumed that the diazonium compound was
obtained by diazotisation of the corresponding amine.

(a) Aniline Yellow: Solvent Yellow 1. It is p-aminoazobenzene.


Aniline yellow is the simplest azo dye and is obtained by
coupling benzenediazonium chloride with aniline in acidic
medium

+
N2Cl - + H NH3 N=N NH2 + HCl

BENZENEDIAZONIUM
CHLORIDE ANILINE YELLOW
(P-aminoazobenzene)

Aniline yellow is used as a dye for oils and lacquers, and is also an
intermediate for other dyes.
23
(b) Butter Yellow: It is p-N, N-dimethylaminoazobenzene.
Butter yellow is obtained by coupling benzenediazonium
chloride with N, N-dimethylaniline.

+ - CH3 CH3
N2Cl + H N N=N N
CH3 CH3
Benzenediazonium N,N-Dimethylaniline Butter Yellow
Chloride (p-N,N-dimethylaminoazobenzene)

Butter yellow has been used for colouring butter, margarine and oils.

(c) Chrysoidine: Basic Orange 2. It is 2, 4-diaminoazobenzene.


Chrysoidine is prepared by coupling benzenediazonium chloride with m-
phenylenediamine.
NH2 NH2

+ -
N2Cl + H NH2 N =N NH2 + HCl

Benzenediazonium m-phenylediamine Chrysoidine


Chloride (2,4-diaminoazobenzene)

Chrysoidine is an orange-red dye. It is used for dyeing paper,


leather, and jute.

(d) Methyl Orange. It is prepared by treatment of helianthine


with sodium hydroxide, whereas helianthine is obtained by coupling
diazotised sulphanilic acid with N, N-dimethylaniline.

+ - CH3
HO3S N2Cl + H N
CH3
Diazotised sulphanilic acid
N,N-methylaniline

CH3
HO3S N=N N NaOH
CH3
Helianthine
CH3
NaO3S N=N N
CH3
Methyl Orange

24
Methyl orange is not a satisfactory dye for textiles because it is
sensitive to acids. It is used as an indicator in acid-base titrations. It is
yellow in basic solutions (above pH 4.4), while red in acidic solutions
(below pH 3.1). This change in the colour is attributed to change in the
structure of its ion. Under alkaline conditions the ion contains the azo
chromophore, while under acidic conditions it contains p-quinoid
chromophore.

Azo p-Quinoid
Compound Chromophore

CH3 H+ +
N=N
N CH3
N -
-
O3S NH N
CH3 OH CH3

Red
Yellow
Acidic Solution
(Alkaline Solution)

(e) Orange II: It is obtained by coupling diazotised sulphanilic


acid with β-naphthol is basic medium.

HO3S
+ -
N2Cl + H HO3S N=N + HCl

HO
Diazotised OH
Sulphanilic Acid Orange 2
-Naphthol

Orange II is used to dye wool, silk, nylon, paper and leather.

(f) Para Red: It is prepared by coupling p-nitrobenzenediazonium


chloride with β-naphthol.

+ -
O2N N2Cl + H O2N N=N + HCl

-Nitobenzene OH OH
diazonium Chloride Para Red
-Naphthol

25
(g) Resorcin Yellow: It is made by coupling diazotised
sulphanilic acid with resorcinol.
OH

+ -
HO3S N2Cl +H OH
OH
Diazolised Reaoroinol
Sulphanilic acid HO3S N=N OH + HCl

Reaoroinol Yellow
Resorcin yellow is used for dyeing silk.
(h) Disperse Red 1: It is obtained by coupling p-
nitrobenzenediazonium chloride with N-ethyl-N- (β-hydroxyethyl)
aniline in acidic medium.
+ - CH2CH3
O2N N2Cl + H N
CH2CH2OH
-Nitrobenzenediazonium N-Ethyl-N-( -hydroxyethyl)aniline
Chloride

CH2CH3
O2N N=N N + HCl
CH2CH2OH

Disperse Red 1

(i) Congo Red. It is a diazo dye, that is, it contains two azo
groups. Congo red is made by coupling tetrazotised benzidine with two
molecules of naphthionic acid.
NH2 NH2
H
H
-+
+ Cl N2 + -
N2Cl +

SO3H Tetrazotised Benzidine SO3H


Naphthionic
Acid

NH2 NH2
N= N N=N
+2HCl
Congo Red
SO3H SO3H

Bismark brown is used for dyeing leather, wool, and cotton.


26
(3) Diphenlymethane Dyes:
Auramine O: It is one of the most valuable of the
diphenylmethane dyes. It is obtained by heating Michler’s ketone with
ammonium chloride and zinc chloride at 160oC.
O

ZnCl2
(CH3)2 C N (CH3)2+ NH4Cl

MICHLERS KETONE

+
NH3

(CH3)2N C N(CH3)2
Cl-

AURAMINE O
Auramine O is used to dye wool, silk, silk, nylon, rayon and paper.

(4) Triphenylmethane Dyes:


Triphenylmethane dyes can be identified by common structural
cature shown below. Notice that the central carbon atom is joined to two
benzene rings and to p-quinoid group.
C

O
Triphenylmethane dyes are not fast to light or washing, however,
except when applied to acrylic fibres. They are used in large quantities

27
for colouring paper, and typewriter ribbons where fastness to light is not
so important.

(a) Malachite Green: It is obtained by condensing benzaldehyde


(1 molecule) with N, N-dimethylaniline (2 molecules) in the presence of
concentrated sulphuric acid to give a leuco base (Gr. Leuco, colourless).
Oxidation of the leuco base with lead peroxide followed by treatment
with hydrochloric acid yields the dye.

H
H N (CH 3)2 H
C==O N (CH 3)2
H N (CH 3)2 C
N (CH 3)2
Benzaldehyde N,N-Dimethyle aniline Leuco base Melachite green
+

N(CH3)2 N(CH3)2
HCl -
C c Cl

N(CH3)2 N(CH3)2

MALACHITE GREEN

Malachite green takes its name from the fact that it has a deep
blue-green colour resembling that a malachite (Copper ore). It is used as
a dye for acrylic fibres, leather, paper, and lacquers.

(b) Pararosaniline: It is the simplest triphenylmethane dye.


Pararosaniline is obtained by consdensinig p-toluidine (1 molecule) with
aniline (2 molecules) in the presence of nitrobenzene to give a colourless
carbinol. Nitrobenzene serves both as a solvent and an oxidising agent.
Treatment of the carbinol with hydrochloric acid yields the dye.

28
H
H NH2 OH NH2
3[O]
H2N C H + H2N C
H NH2 -2H2O NH2
H
Aniline Colourless carbinol
p-toludine

HCl NH2
-
H2N C Cl
-H2O
NH2

PARAROSANILINE

Pararosaniline has been used to dye cotton, wool and silk.

(c) Rosaniline: Fuchsine, magenta. It is closely related to


pararosaniline. Rosaniline is prepared by condensing one molecule each
of aniline, p-toluidine, and o-toluidine in nitrobenzene to give a carbinol.
Treatment of the carbinol with hydrochloric acid yields the dye.

H
H NH2 OH NH2
3[O]
H2N C H + H2N C
H NH2 -2H2O NH2
H
Colourless carbinol CH3
p-toludine CH3
O-Toluidine
+

HCl NH2
-
H2N C Cl
-H2O
NH2

CH3

PARAROSANILINE

29
Rosaniline has a greenish metallic lustre. It dissolves in water to
give a deep-red colour. Rosaniline is used for dyeing cotton, silk and
wool. Addition of sulphur dioxide to the dye solution produces the
colourless Schiff’s reagent, which is used to test the presence of
aldehydes.
(d) Crystal Violet: It is obtained by condensing Michler’s ketone
with N, N-dimethylaniline in the presence of phosphorous oxichloride
(POCl3) or phosgene (COCl2). If phosgene is used, then crystal violet can
be prepared directly by heating phosgene and N, N-dimethylaniline, since
these two react to give Michler’s keton.
POCl3
(CH3)2N C O + H (NCH3)2
or COCl2

N,N-DIMETHYLE ANALINE

N(CH3)2 +

MICHLERS KETONE

c N(CH3)2 -
Cl

CRYSTAL VIOLET
Crystal violet has a greenish-brown metallic lustre. It dissolves in water
to give a deep-blue colour. Crystal violet is used in the manufacture of
inks, stamping pads, and typewriter ribbons. It is also used as an
indicator for the determination of hydrogen-ion concentration of
solutions.
(5) Xanthene Dyes:
Xanthene dyes can be identified by a common structural feature
shown below. They are obtained by condensing phenols with phthalic
anhydride in the presence of zinc chloride, sulphuric acid, or anhydrous
oxalic acid. Examples of this class are fluorescein, eosin, and rhodamine B.
O
O

30
(a) Fluorescene. It is prepared by heating resorcinol (2
molecules) and phthalic anhydridge (1 molecule) with zinc chloride at
190oC
HO
O OH
HO
OH OH OH
C NaOH
ZnCl2
O
H H O
O 2H2O C
CH2
C O

FLUORESCEIN

PATHALIC ANHYDRIDE
OH O O

COONa+

URANINE

Fluorescein is of no value as a dye. It is red powder, which is


insoluble in water. A dilute solution of fluorescein in sodium hydroxide
gives a strong yellow-green fluorescence when exposed to light. It is
used to trace pollution of water supplies by sewerage, since if a small
quantity of it is put in at the suspected source of pollution, the colour will
be detectable at some distance from the source, even after extensive
dilution. During World War II, fluorescein was used as a sea marker for
airmen who had to bail out from aeroplanes over water. It also aided
searchers in locating them. Fluorescein is also used as a mild purgative.
The sodium salt of fluorescein is called Uranine. It is used to dye wool
and silk.

(b) Eosin: It is the sodium salt of tetrabromofluorescein. Eosin


is obtained by brominating fluorescein in glacial acetic acid to give
tetrabromofluorescein. Treatment of this with sodium hydroxide yields
the dye.

31
HO Br
O OH Br

Br2 HO O OH NaOH
C
O
CH3COOH Br C Br
C o O
C o

FLUORESCEIN
Tetrabromofluricine

Br
Br

Nao O O

Br Br
COONa+

Eosin is a EOISNE
red solid, which is soluble in water. Alkaline solutions of eosin show a
yellow-green fluorescence. Eosin is used for dyeing wool, silk, and
paper; for making red ink and as the colouring matter in lipsticks and nail
polishes.
(c) Rhodamine B: It is prepared by condensing phthalic
anhydride with N,N-diethyl-m-aminophenol in the presence of zinc
chloride, and treating the product with hydrochloric acid.
----
(C2H6)2N OH H-O N(C2H6)2 (C2H6)2N
+ O N(C2H6)2

HO H HCl
ZnCl2 C
C O O
C=O
C=O - 2H2O

+
PATHALIC ANHYDRIDE

(C2H6)2N N(C2H6)2
-
Cl
C

COOH

RHODAMINE B

Rhodamine B is used for dyeing silk, wool and cotton.


32
(6) Phthaeleins:
Phthaleins are related to xanthene dyes and are made in the same
way.
Phenolphthalein: It is prepared by condensing phenol (2
molecules) with phthalic anhydride (1 molecule) in the presence of zinc
chloride at 120oC.
OH
OH
OH
HO
H H ZnCl2
O
O C O
-H2O
C CO C=O

Phthalic Anhydride Phenolphthalein


(Colourless)
Phenollphthalein is not a dye. It is colourless solid, mp 261oC.
Phenolphthalein is insoluble in water, but dissolves in alkalis to form
deep red solutions. This is due to the formation of a disodium salt, the
ion of which is coloured because of resonance. When excess of strong
alkali is added, the solution of phenolphthalein becomes colourless. This
is attributed to the formation of a trisodium salt, the ion of which is
colourless because of loss of resonance and quinoid structure.
OH
HO
O -
ONa+ + - O
NaO
-
OH
C O
C O H+ C
- C + -
COONa+ COONa

Sodium Salt
Phenolphthalein (Red)
(Colourless)

-
H+ OH

+
NaO- - +
ONa
OH
O
+
COONa

Trisodium Salt
(Colourless)

33
Because of the colour changes shown above, phenolphthalein is
used as an indicator in acid-base titrations.
Phenolphthalein is an extremely powerful laxative, and this
accounts for its widespread use as a denaturant for laboratory alchohol.

(7) Indigoid and Thioindigoid Dyes:


Indigoid. It is the parent compound of indigoid dyes and has been
used in this country from times immemorial. Egyptian mummy clothes,
which are 5000 years old, were dyed with it. Indigo was originally
obtained from plants of indigofera group. The leaves from these plants
were covered with water and allowed to stand for several hours.
Enzymes present in the plants brought about fermentation, as a result of
which the β-glucoside of indoxyl (known as indican) in the leaves was
converted into indoxyl and glucose. Upon exposure to air the indoxyl
was oxidised to indigo.
H
N
CH
C
CH2OH O
O OH C
Fermentation H H
OH H + CH2
O OH H N
CH2OH H OH
H
H -D-Glucose Indoxyl
H
OH H
OH -Link
H OH H
H
O
O N
C C
Oxidation C C
CH2 C
N N
O
H H Indigo
Indoxyl
(Indican)
Natural indigo contains an isomer of indigo known as indirubin
(Indigo Red), and other impurities in varying proportions. Most of the
indigo used at the present time is a synthetic product. It has replaced the
natural stuff because of cheapness, purity, and uniformity of the
manufactured dye.

34
Preparation of Indigo. It may be obtained:
(1) By Heumann’s First Indigo Synthesis (1890). This involves
the condensation of aniline with chloroacetic acid to give N-
phenylglycine. The phenylglycine is then fused with sodium hydroxide
and sodamide at 250oC to form indoxyl, which on oxidation by air yields
the dye.
O
HO HO O
H C O C
C HaOH + NaNH2
+ H
CH2 CH2
+
H CH2 N
N
Cl N Indoxyl
Aniline Chloro Acetic Acid O2 H
H
H
N-Phenylolycine
H
O

C N
C C
N C
O
H
Indigo
(Indigotin)

N-Phenylglycine is now obtained in much higher yield by interaction of


aniline and the bisulphite compound of formaldehyde at 50-60oC,
followed by treatment with aqueous sodium cyanide, and hydrolysis of
the resulting nitrile.
O OH

H C + NaHSO3
H H C H
Formaldehyde Sodium
Bisulphite -
SO3Na+
An Addition
Product

- + - +
SO3Na SO3Na
+ 50 70OC NaCN
N H HO C H CH2 -Na2SO3
N
H H
H

HO O

C N C
H+
CH2 H2O CH2
N N

H H
N-Phenylglycine
35
(2) By Heumann’s Second Indigo Synthesis (1896): This
involves the condensation of anthranilic acid with chloroacetic acid to
form N-phenyl-o-carboxylic acid. This is then fused with sodium
hydroxide and sodamide to produce unstable indoxylic acid, which
decarboxyhlates to give indoxyl. Oxidation of indoxyl by air yields the
dye.
OH
OH
C O
C
CH2 COOH O
+ CH2 COOH
Cl
N H
Chloroacetic acid N
H H
Anthranilic Acid N-Phenylglycine-o-carboxylic acid

OH
O
-H2O C CO2 C
O2
NaOH, NaNH2, C CH2 Indigo
N COOH N
H H
Indoxylic acid Indoxyl
(unstable) (2 molecules)

(3) From Aniline and Ethylene Oxide (1943): This involves


treatment of aniline with ethylene oxide to form N-phenyl-2-
hydroxyethylamine with sodium hydroxide and sodamide at 200oC
produces its disodium derivative. The sodium derivative is heated rapidly
to 300oC and then cooled to 240oC to yield the sodium salt of indoxyl.
This on treatment with water and oxidation by air give indigo.
O CH2 OH
+ NaOH + NaNH2
H2C CH2 CH2
NH2
N 200 0C
Aniline Ethylene Oxide
H
N-Phenyl-2-hydroxyethylamine

-
CH2 ONa+
C -ONa
+
CH2 (1) 300 OC C OH
N- (2) 240 OC CH H2O
Na+ N CH
N
Indoxyl
Sodium Salt of indoxyl H
H (Enol form)

36
O
C
CH2 Indigo
N

H
Indoxyl
(Keto form) Indigo is a dark-
o
blue crystalline compound, mp 390-2 . It is insoluble in water and most
organic solvents, but soluble in aniline, nitrobenzene, and chloroform. It
can be sublimed under reduced pressure to deep red vapours, which on
cooling yield prismatic crystals. Indigo is used very extensively for
dyeing cotton by the Vat Process, and in printing inks.

Structure of Indigo: The structure of indigo has been deduced from


consideration of facts and conclusions such as the following.
1. Elemental analysis and molecular weight determinations show
that the molecular formula of indigo is C16H10O2N2.
2. Fusion of indigo with sodium hydroxide at low temperature
produces anthranilic acid. This indicates the presence of a benzene ring
attached to one carbon atom and one nitrogen atom in the ortho position.
O

C OH
Indigo NaOH

NH2

Anthranilic Acid
3. Oxidation of indigo with nitric acid yields only two molecules
of isatin. This indicates that the indigo molecule contains two identical
units joined together, and that each unit on oxidation produces a
molecule of isatin.

2[O] C=O
INDIGO
C=O
N

H
Isatin
37
The following two possible structures of indigo meet this
requirement.
O O
C C C C
C C C C
N N N O O N

H H H H

(A) (B)

4. Oxidation of indoxyl by air yields indigo.


O
O2 O O
C C C
CH2 C C
N N N

H H H

INDOXYL INDIGO
From above, it follows that (A) represents the structure of indigo. This
has been confirmed by the following synthesis by Baeyer (1872).
O O O
C C C
PCl5
C C C
N O N OH N Cl
H
Isatin Isatin chloride
Isatin (Enol form)
(Keto form)
Zn CH3COOH

OO O
C C C
O2
C C CH2
N N N
Indigo
H H H
Indoxyl
Two geometrical isomers are possible for (A) (Two Molecules)

H
O O O
C C C N
C =C C =C

N N N C

O
H H H

Cis-form Trans-form

38
X-Ray analysis shows that mostly indigo exist in the more stable trans-
form. However, derivatives of both are known.

(a) Tyrian Purple. It is 6, 6’-dibromoindigo. Its discovery was


later than that of indigo but it is believed to have been known in 1600
BC.
O H
4 3 1' 7'
Br
C N
6'
C C
2 2' 5'
N C 3'
Br 6 7 4'
H O
Tyrian Purple
(6,6' - Dibromoindigo)

Tyrian purple occures naturally in the purple snail, Murex


Brandaris. It takes about 12000 snails to produce 1.4 g of the dye. This
explains its rarity and why the colour of mercial value.

(b) Thioindigo. It is analogues to indigo in which the two –NH–


groups are replaced by sulphur atoms. Thioindigo may be obtained by
the reaction of thiosalicylic acid, with chloroacetic acid, followed by
fusion with sodium hydroxide and oxidation by air. Thiosalicylic acid
itself is made by diazotisation and reaction with hydrogen sulphide.
COOH
COOH COOH
1. Diazotize COOH
ClCH3COOH HaOH
2. H2S
NH2 200 0C
SH S CH2
Anthranilic Thiosalicylic
Acid Acid
OH O
O
C C S
C
CH O2
C C
CH2
S S C
S
Thioindoxyl Thioindoxyl O
(Enol-Form) (Keto-Form) THIOINDIGO

Thioindigo is used to dye cotton, wool and polyesters.


39
(8) Anthraquinoid Dyes:
Anthraquinoid dyes can be identified by a common structural
feature shown below. Notice that a p-quinoid group is fused to two other
benzene rings.
O

O
Anthraqluinoid dyes are used for dyeing wool, silk, nylon, cotton,
leather and paper. The most important dye in this group is alizarin.
Alizarin. It is 1,2-dihydroxyanthraquinone. Alizarin derives its
name from the fact that it was first obtained from the roots of the madder
plant (Fr. Alizari, madder). It is now prepared from phthalic anhydride by
the following six steps.
Step 1. Phthalic anhydride is treated with benzene in the presence
of AlCl3 to give o-benzoylbenzloic acid. (Friedel-Crafts Reaction)
o O
c
C
o AlCl3

c OH
C
o
O
O-Benzoyl-Benzoic Acid
Step 2. O-Benzoylbenzoic acid is cyclized by treatment with
concentrated sulphuric acid to form anthraquinone.
O O
C
H2SO4
OH
C
H
O
O Anthraquinone
Step 3. Anthraquinone is heated with fuming sulphuric acid at
o
180 C to give anthraquinone-2-sulphonic acid.
40
O O
SO3H
+ H2SO4
Fuming

O O
Anthraquinone Anthraquinone
Anthraquinone-2-sulphonic acid
Step 4. Anthraquinone-2-sulphonic acid is converted into its
sodium salt by treatment with sodium hydroxide.
O
O
SO3H
SO3Na
NaOH

O
Anthraquinone O
Anthraquinone-2-sulphonic acid Sodium salt of
anthraquinone-2-sulphonic acid
Step 5. Sodium salt of anthraquinone-2-sulphonic acid is fused
with sodium hydroxide in the presence of potassium chlorate at 200oC
under pressure to give sodium salt of 1, 2-dihydroxyanthraquinone. The
purpose of potassium chlorate is to provide oxygen for the oxidation of
the carbon atom at C-1.
- +
O O ONa
8 9 - + +
-ONa
7 SO3Na
2
+ Na2SO4
6 3
5 10 4 + 2H2O
O O

Sodium salt of
1, 2-dihydroxyanthraquinone
Step 6. Sodium salt of 1,2-dihydroxyanthraquinone is treated with
sulphuric acid to yield 1,2-dihydroxyanthraquinone (Alizarin).
O ONa
O OH
ONa
OH
H+

O
O
Alizarin
(1, 2-dihydroxyanthraquinone)
Alizarin can also be made by condensing phathalic anhydride with
catechol in the presence of sulphuric acid at 180oC (See Below).

41
Alizarin forms ruby red crystals, mp 290oC. It is insoluble in water
and ethanol. It dissolves in alkalis to give purple solutions. Alizarin is
used to dye cotton and wool. It is also used for making printing inks.

Structure of Alizarin:
The structure of Alizarin has been deduced as follows:

1. Elemental analysis and molecular weight determinations show that


the molecular formula of alizarin is CI4H3O4:

2. Reduction of alizarin with zinc dust at 400oC produces anthracene.


This indicates that it has the same carbon skeleton as that of
anthracene.

3. Alizarin reacts with acetic anhydride to form a diacetate. This


indicates the presence of two hydroxyl groups in the molecule.

4. Alizarin can be prepared by condensing phthalic anhydride and


catechol in the presence of sulphuric acid at 180oC. This shows
that alizarin is a dihydroxy derivative of anthraquinone and both –
OH groups are substituted in the same benzene ring.
O OH O OH
OH
C OH
H2SO4
O +
C
Catechol
O O
Phthalic anhydride Alizarin
(1,2-dihydroxyanthraquinone)

The above facts limit our choice to two structural formula for alizarin.
O OH O
OH OH

OH
O
O
(A) (B)

42
5. Alizarin on nitration yields two isomeric mononitro derivatives,
both of which on oxidation give phthalic acid. This shows that in
each of these derivatives, the – NO2 group is substituted on the
hydroxylated benzene ring.
Let us now write down the possible mononitro derivatives from
(A) and (B).
Mononitro derivatives from (A):
O OH O OH
OH OH

NO2

O O NO2
DIFFERENT

MONO TRO DERIVATIVES FROM (B)

O
O NO2
OH
OH

OH
OH
O NO2
O

IDENTICAL
Since only formula (A) permits the formation of two isomeric
mononitro derivatives, it represents the structure of alizarin.

(A) CLASSIFICATION ACCORDINGTO METHOD OF


APPLICATION:
Methods for dyeing vary with the chemical structure of the fibre
to be dyed. A dye suitable for wool or silk may be entirely unsatisfactory
for dyeing cotton or rayon. Wool and silk are protein substances. They
contain many acidic and basic (polar) groups. These groups serve as
points of attachment for a dye because it also has acidic or basic group.
On the other hand, cotton and rayon fibres are composed of cellulose in
quite pure form and provide only neutral ether linkages and hydroxyl
groups as points of attachment for hydrogen bonds. Polyolefin fibres are
formed from products of polymerisation of unsaturated hydrocarbons, for
43
example, propylene. They do not contain any polar groups and require
still other techniques for dyeing.
As already mentioned, a dye must do more than simply colour the
surface of the fibre. It should become part of the fibre, and wear and
wash with the fibre. A dye should be fast to light and should show
resistance to the action of various organic solvents used in dry-cleaning,
dilute alkalis and acids, etc. A number of dyes satisfy these conditions
very well when used on some material but not when used on others. In
all cases chemical structure of the material determines the process and
the dye to be used for dyeing it. A number of dyeing methods and dyes
adaptable to each method are described below.

1) Direct Dyes:
These contain acidic or basic groups and combine with polar
groups in the fibre. Such dyes colour a fabric directly when the
fibre is immersed in a hot aqueous solution of the dye. Direct dyes
are used to dye wool and silk. Two examples of this class are
Naphthol Yellow S and Martius Yellow. Both compounds are
acids and combine with the free amino groups present in wool and
silk fibres. Synthetic polyamide fibres (Nylon) can also be dyed by
this method.

2) Mordant Dyes:
This class of dyes requires a pretreatment of the fibre with a
mordant material designed to bind the dye. The mordant becomes
attached to the fibre and then combines with the dye to form an
insoluble coloured complex. This complex is called a lake.
Commonly used mordant are the oxides of aluminium, iron and
chromium. Mordant dyes may be used to dye wool, silk and
cotton. Alizarin is an example of a mordant dye. It gives different
colours when used with different mordants. It gives a red colour
with aluminium and tin salts, brownish red tones with a chromium
mordant, and black-violets with an iron mordant.

44
fibre

O OH o
o
Al

OH O OH
Al3 + fibre
+

Modarant mordant dyes on fibre

dyes have been used for many centuries. They have lost their
original importance because their use is no longer necessary.
Equal or superior results can be obtained with other classes of
dyes at less expense in time and labour.

3) Vat Dyes:
These dyes are insoluble in water, but on reductin with sodium
hydrosulphite yield alkali soluble forms (Leuco-compounds)
which may be colourless. It is in this form they are introduced
into the fabric. The reducing operation was ormerly carried out in
wooden vats, giving rise to the name ‘Vat Dyes’. After the
reduced dye has been absorbed in the fibre, the original insoluble
coloured dye is reformed by oxidation with air or chemicals. Vat
dyes are used to dye cotton, and very fast because of their
insolubility in water. Indigo is an example of a vat dye.
O H OH H

C N C N
Reduction
C C
C C
Oxidation N C
N C
OH
O H
H INDIGO COLORLESS
INDIGO BLUE WATER INSOLUBLE WATER SOLUBLE

4) Ingrain Deys:
These dyes are synthesised within the fa bric, and may be applied
to any type of fibre. The azo dyes are good examples of ingrain
dyes. The cloth to be dyed is first soaked in an alkaline solution
45
of a phenol (usually naphthol) and dried. It is then immersed in a
cold alkaline solution of a diazonium salt. Coupling reaction takes
place within the fabric. Since these dyes are insoluble in water,
they are very fast.

5) Disperse Dyes:
These are insoluble in water, but are capable of dissolving certain
synthetic fibres. Disperse dyes are usually applied in the form of a
dispersion of finely divided dye in a soap solution in the presence
of some solublising agent such as phenol, cresol, or benzoic acid.
The absorption into the fibre is carried out at high temperatures
and pressures. Disperse dyes are used to dye acetate rayons,
Dacron, Nylon and other synthetic fibres. Celliton Fast Pink B (1-
amino-4-hydroxyanthraquinone) and Celliton Fast Blue B (1,4-N,
N’ –dimethylaminoanthraquinone) are examples of disperse dyes.

NH2 H
O
o N-CH3

O OH
CELLITON FAST PINK B o N-CH3

H
CELLITON FAST BLUE B

46
Dyes & Fibre Polymer System 4
Wool Fibres:
The wool fibre is composed of the protein keratin, which consists
of long polypeptide chains built from eighteen different amino acids.
Most of these acids have the general formula H2N.CHR.COOH, in which
R is a side chain of varying character. The chain structure is of the type:
H
R2
H
NH CO
CO C C
NH NH CO
C
H
R3
R1
And at intervals bridges derived from the amino acid cystine connect the
chains. Some of the side chains end in amino groups and others in
carboxyl groups; internal salts are therefore formed and the
H2N COOH
CH2 CH
CH CH2 S S
NH2
HOOC

Molecules are bound together by electrovalent linkages. The molecules


of keratin are very large, with and average molecular weight estimated at
about 60,000.
The wool fibre is readily destroyed by alkali, but withstands acid
conditions fairly well; some hydrolysis of peplide linkages occurs on
prolonged boiling with acids, however. The carboxylic acid and amino
groups in the keratin molecule confer affinity for basic and acid dyes.
Basic dyes are now little used on wool since their fugitive properties
render them unsuitable for such and expensive and durable fibre. Acid
dyes, however, are extensively used, and the general characteristics of
this large class and the related mordant and pre-metallised azo dyes are
now described.
47
Since the bonds between dye anions and amino groups in the wool
fibre are easily broken and re-formed, dyes attached in this way are liable
to migrate. This property is advantageous, in that level dyeing is readily
attained, but it leads to low fastness to wet treatments, and any undyed
wool present during washing becomes stained. These characteristics are
chiefly apparent in dyes of low molecular weight, and fastness to
washing is in general much better in more complex dyes. The larger dye
molecules are evidently attached the fibre by some means other than the
ionic bonds mentioned above, and it is believed that6 they are held by
non-polar van der Waals forces exerted between hydrophobic dye anions
and hydrophobic regions of the wool fibre, their strength being
proportional to the area of contact.
From an application point of view acid dyes are classed as either
Levelling or Milling types. The Levelling (sometimes called Equalizing)
dyes have fairly simple chemical structures, migrate readily on wool, and
are easily applied from strongly acid baths; their wet-fastness properties
are low. The Milling dyes are structurally more complex, have high
affinity, and must be applied form weakly acid baths for control of the
rate of dyeing, but they show high fastness to milling and other wet
treatments. Milling is a felting process applied to woolen cloth by
squeezing or beating, usually in a soap solution. It sometimes follows
dyeing, and the dyes used must then have high wet-fastness properties in
order to withstand these severe conditions.
The advantages of good levelling and high milling fastness cannot
be fully combined in a single dye, but there are general purpose dyes
with intermediate GTFVJ,./properties. The application classes can be
correlated roughly with chemical types, as shown for monoazo and
disazo dyes in Table 4 – 1, which provides a few typical examples. As
might be expected from the foregoing generalizations, trisazo and other
polyazo dyes are of the milling class, but since shades are usually dull
and uneven they are seldom of technical value on wool.

Silk Fibres:
Cultivated silk is a natural fibre produced by larvae of the
silkworm Bombyxmori, and wild silk is produced similarly by
silkdworms of various species. Raw silk consists of the protein fibroin
surrounded by silk gum (sericin), and the latter is removed in the process
48
of de-gumming or ‘boiling off’ which precedes dyeing. Fibroin consists
of long parallel chain containing about 400 amino acid residues with a
structure of the general type
R

CO NH CH CO NH CH CO
NH CH

. R
The residues are derived mainly from the amino acids glycine (R
= H), alanine (R = CH3), serine (R=CH2OH) and tyrosine (R= --CH2---
OH), but there are numerous others in small quantities. Fibroin differs
from keratin in that it contains no sulphur. Its chemical properties are
similar to those of keratin, but it is more sensitive to acids than the latter
and less sensitive to milk alkalis. Silk can be dyed with dyes of almost
every class, but some restrictions arise from the common practice of
weighting the fibre with tin salts, which is carried out in order to improve
handling properties and reduce cost.
So far as azo dyes are concerned the main classes applied to silk
are the acid dyes and pre-metallised dyes already described as wool dyes,
the direct dyes described in Chapter and the reactive dyes described in
Chapter. Mordant dyes applied to silk are mainly of the anthraquinone
type. It has never been necessary to develop dyes especially for silk.

Cellulosic Fibres:
The earliest cellulosic fibres were lines and cotton, both of which
have been used since remote antiquity. Linen, or flax, is derived from
‘bast’ fibres of plants of the Linum family, especially Linum
usitatissimum. After removal of glutinous and pectinous matter the fibre
has cellulose content of 82 – 83%. Cotton, which is fine hair attached to
seeds of various species of plants of the Gossypium genus, has a
cellulose content which may reach 96%. Cellulose is a polymer of high
molecular weight consisting of long chains of D-glucose units connected
by B-1, 4- glucosidic bonds, and its structure may be represented as
follows:

49
Each glucose unit contains three alcoholic hydroxyl groups, of which
two are secondary and one is primary. The degree of polymerisation of
cellulose varies from a few hundred to 3500 or more.
Regenerated cellulose fibres were introduced during the last two
decades of the 19th century. The first process was that Chardonnet
(1884), who produced a fibre by spinning a solution of nitrocellulose in a
mixture of alcohol and ether and subsequently removing nitro groups.
The cuprammonium process followed (1890), and in 1891 Cross and
Bevan introduced the viscose process whereby wood pulp cellulose is
treated with caustic soda and carbon disulphide to form sodium cellulose
xanthate, which, after a ‘ripening’ stage, is spun into an acid coagulating
bath. The nitrocellulose process is now obsolete, but the cuprammonium
process, which has the advantage of giving an exceptionally fine
filament, is still used. The viscose process is of much greater importance,
but it is declining in consequence of the development of the newer
synthetic fibres.
The dyeing properties of the various cellulosic fibres are broadly
similar, but application conditions are affected by differences in
physically properties. Thus lines, which has a harder structure than
cotton, is less readily penetrated by dyes. There are also differences in
dyeing properties between the several types of regenerated cellulose
fibres; cuprammonium rayon, for example, having fine filaments, is more
easily dyed than viscose.
Dyes of many chemical classes are applied to cellulosic fibres.
Azo dyes, which predominate numerically, are described here, and others
are dealt with in the appropriate chapters.
The first substantive or ‘direct’ dyes discovered in 1884 were
diazo dyes obtained from tetrazotised benzidine, but other structure have
since been found to confer affinity for cellulose. The azo group itself
favours substantivity but for adequate effect either a second azao group
or another favourable group must also be present in the dye molecule.

50
The structures which are chiefly important in substantive dyes are as
follows:
CONH
N= N

AZO DIPHENYLE CARBOXYAMIDE

NaO3S
NH2
CH=CH

STILBENE HO

J-ACID
NaO3S
S
HC
CH
CH
NH2 N

HO THAIZOLE

GAMMA ACID
All of the other groupings listed find used in conjunction with the azo
chromophore to give a great variety of dyes for cellulosic fibres. Others
of smaller importance, such as the residues of pyrazol-5-one, resorcinol
and m-phenylenedianine, also confer a measure of cellulose affinity.
Apart from the presence of one or more of the favourable components
there are other structure requirements for substantivity.
Typical substantive azo dyes of the various chemical classes are
now described.

Monoazso Dyes:
About 35 monoazo direct dyes are in use, most of them containing
either a thiazole or a J acid residue. Examples are CI Direct Yellow 8
(CI 13920), CI Direct Brown 30 (CI 17630) and CI Direct Red 118 (CI
17780) (diazotised and developed on the fibre with B-naphtol or 3-
methy-1-phenylpyrazol-5-one), with the structures shown:

51
NaO3S
HO
H3C
S C-CH3
C N=N-C

N CONHPh
CI DIRECT YELLOW 8
NaO3S
H3C
NaO3S
S
S
C C
N N=N NHPh
N

HO
CI DIRECT BROWN 30
NH2

NaO3S NHCO

N=N CI DIRECT RED


118
HO
Congo Red, the first direct dye manufactured, which was discovered by
Bottiger in 1884, has the constitution benzidine (naphthionic acid) and is
therefore included under this heading. Many other dyes of the same.

Dyes with Mixed Chromophores:


Polyazo dyes normally contain a single chromophoric system, and
a conjugated chain runs through the whole molecule. It is possible,
however, for a dye molecule to contain two or more independent
chromophoric systems electronically insulated from each other. Such
dyes were first introduced by CIBA, who utilized the triazinyl ring as a
chromophoric block. This ring serves as a convenient link since it can be
introduced by reaction of cyanuric chloride with two or three amino-
containing dyes in succession. Substitution of the first chlorine atom
52
takes place easily in presence of alkali at atmospheric temperature. The
second chlorine atom is less easily removed, and reaction with an amino
compound may require a temperature of 55o – 60oC, the optimum
conditions varying with the basicity of the amine. Replacement of the
clorine atom calls for still more vigorous conditions, and a temperature
of 90o – 100oC may be suitable; much higher temperature are needed,
however, in the case of weakly basic compounds. The progressive loss of
activity at each stage enables condensation to be carried out with three
different components to give a substantially homogeneous product. The
residues of three dyes (Dye 1)-NH2, (Dye 2)-NH2 and (Dye 3)-NH2 may
be linked by a series of reactions in alkaline medium, as shown:
Stage 1 Cl
N

(Dye 1) NH2 + Cl N Low

N Temperature
Cl Cl
N
Stage 2
(Dye 1) NH N
Cl
N
N
Cl
(Dye 1) NH N
Moderate
+ (Dye 2) NH2
N Temperature NH (Dye 2)
Cl N

(Dye 1) NH N
N
Cl
Stage 3
NH (Dye 2)
N

(Dye 1) NH N + (Dye 3) NH2 High


Temperature
N
Cl
NH (Dye 2)
N

(Dye 1) NH N

N
NH (Dye 3)

In the resulting product each dye residue contributes its own absorption
characteristics; by combining yellow and blue components, green dyes
can therefore be obtained that are much brighter than normal polyazo
greens. Dyes containing three inde; pendent chromophoric system is of
limited interest and the third condensation is often carried out with a
suitably reactive colourless compound such as aniline or phenol.
53
An example of a commercial dye containing two electronically
insulated chromophores is Chlorantine Fast Green BLL (CIBA) (CI
Direct Green 26; CI 34045); it gives bluish green hue on cellulosic
fibres. One of the aminoazo dye residues. A commercial dye containing
both azo and anthraquinone residues is Chlorantine Fast 5 GLL (CIBA)
(CI Direct Green 28; CI 14155), which has the structure (2) and gives
bright yellowish green shades on cellulosic fibres.
NaO3S

OH NHPh
OMe COONa
N N
N N NH NH N N OH
N
NaO3S Me

(1)

NHPh
O O SO3Na
COONa
N N
H2N NH HN NH- -N=N- OH
N
S
O3
Na

(2)

Cellulose Acetate Fibres:


The D-glucose units in the cellulose polymer contain three
hydroxyl groups, of which one is primary and two are secondary. By
acetylating all of the hydroxyl group in cellulose a triacetate is obtained
with a polymetric structure which may be represented thus:
OAc

H OAc
CH2

H H O
o OAc H
H
OAc H
H
O
H O H

H n
OAc
CH2

OAc

54
The triacetate is soluble in chloroform, and a fibre known as
Lustron was spun from chloroform solution in early small-scale
American manufacture (1914-1924). If the triacetate is partially
hydrolysed to give a mixture with an average of 2 ½ acetyl groups per
glucose residue the product loses solubility in chloroform, but becomes
soluble in acetone. A different product, which is insoluble in acetone, is
obtained by direct introduction of 2 ½ acetyl groups; presumably the less
accessible hydroxyl groups are the last to be acetylated and the last to be
re-formed on hydrolysis.
During the First World War incompletely acetylated cellulose was
produced on a large scale for use as a dope for aircraft fabric. After the
war efforts to find a new use for it led to the production of cellulose
acetate fibre by British Celanese Corporation. The commercial product
contains an average of 2-3 acetyl groups per glucose residue, and is
known as secondary acetate, or simply ‘acetate’. It is spun from acetone
solution. In spite of an inconveniently low melting-point acetate fibre
attained great success and is still extensively used, but in recent years it
has been partly superseded by other synthetic fibres.
It was appreciated in the early days that the dyeing of acetae differs
from that of the natural fibres and viscose in that fibre serves as a solvent
for the dye. In 1923 work on dyes in the form of aqueous dispersions was
carried out independently by British Celanese Corporation and British
Dyestuffs Corporation. The SRA colours of British Celanese Corporation
were dispersions of aminoazo or hydroxyazo dyes obtained by means of the
surface-active agent sulphated ricinoleic acid. Other dispersing agents used
included alkyl sulphates, alkaryl sulphonates and fatty alcohol-ethylene
oxide condensates (a long alkyl chain being usually present in the
molecule), and the dispersions obtained by applying them with various
milling techniques were often so fine as to be easily mistaken for true
solutions. British Dyestuffs Corporation marketed dispersed aminoazo and
hydroxyazo dyes in their Dispersol range, and this is still maintained by ICI
(formed in 1926 by a union of British dye stuffs Corporation with other
firms). The Duranol range is a parallel range of dispersed dyes of the
anthraquinone series.
Dyes of these types are now produced by many manufactures.
Whereas the dyes were formerly supplied only as aqueous dispersions

55
they are now usually marketed in the form of re-dispersible powders
which yield suitable dispersions on stirring with water.
Hydroxyalkylamino groups impart a small degree of water-
solubility and assist dispersibility; coupling components such as N-ethyl-
N- B-hydroxyethylaniline or N, N-di (B-hydroxyethyl) aniline are
therefore commonly used. Many of the earlier yellow and orange dyes
proved to be phototropic, but it was found that this groublesome
characteristic can be largely avoided by introducing nitro or other
negative groups into the dye molecule; these substituents restrain trans
cis isomerizatrion. Since dye molecules must be fairly small in order that
they dissolve readily in the fibre monoazo dyes are commonly used, but
a few disazo dyes are included in commercial ranges. Blacks are
obtained by diazotising aminoazo dyes on the fibre and developing with
a solution of 3-hydroxy-2-naphthoic acid.
In 1936 a range of water-soluble dyes for acetate was marketed by
ICI under the name Solacet. Their solubility was due to the presence of a
sulphuric ester group (-- OSO3Na), usually introduced by sulphation of a
B-hydroxyethlamino group, which did not seriously impair affinity for
the fibre. The unsuitability of conventional water-soluble dyes for acetate
fibres is apparently due to the presence of highly ionised – SO3-Na+
groups rather than their solubility in water. In consequence of the of the
development of dispersed dyes with improved dyeing and fastness
properties the Solacet range has now been superseded.
Many dyes developed for acetate have now been applied to the
newer synthetic fibres, and the manufactured ranges have been extended
specially for these outlets. The term ‘Acetate dyes’ has therefore, been
discarded in favour of ‘Disperse dyes’ so that all applications may be
included. Disperse dyes for fibres other than acetate are described later.
Examples of azo disperse dyes applied to acetate are shown in Table 4.6;
violet and blue dyes are included, but disperse dyes of these shades are
derived mainly from the anthraquinone series.

Cellulose Triacetate Fibres:


Cellulose triacetate was manufactured in the United States during
the period 1914-24, but the process was unsatisfactory because the only
suitable solvent then commercially available was chloroform, and this
was both toxic and expensive. Methylene dichloride is a suitable solvent
56
of low toxicity, and it became available fairly cheaply about 1930, but by
the eat time secondary acetate was fully established. Later, however,
when the hydrophobic fibres nylon and ‘Terylene’ had achieved great
success, the possibilities of triacetate as an inexpensive fibre sharing
some of their good properties became apparent, and it has now been
introduced as a commercial fibre under names such as Tricel (Courtaulds
Ltd.), Armel (Celanese Corporation of America) and Trilon (Canadian
Celanese Ltd.). It has good shrink- and crease-resistance, is quickdrying,
shows good fastness to wet treatments and can be heat-set without loss of
lustre. As it has a higher melting point the hazards associated with the
ironing of fabrics of secondary acetate are largely avoided.
Because of its hydrophobic character triacetate is less easily dyed
than acetate, but suitable dyes can be selected from existing ranges of
disperse dyes. Whereas acetate is dyed at 75o–80oC, triacetate requires a
temperature at or near the boil. If the fabric is to be heat-set for pleats
the dyes used must be stable at 200oC.

Poyamide Fibres:
Nylon 6,6 and Nylon 6 can be dyed by many disperse, acid and
direct dyes. Since many suitable dyes are available, commercial ranges
are usually selected from products already manufactured for other
purposes, and (apart from the reactive dyes discussed later) new
structures have not been required. It has proved very difficult to
manufacture nylon with uniform dyeing properties, and for this reason
dyes with good leveling properties are necessary. In this respect disperse
dyes have a great advantage in that they conceal fibre irregularities. For
high wet-fastness acid dyes are preferred, but very careful application is
necessary in order to secure level dying. These dyes often show better
wet-fastness properties on nylon than on wool because of the
hydrophobic character of the former. Fastness to light, however, is often
slightly lower on nylon than on wool. The affinity of acid dyes for Nylon
6 is higher than that for other types because polycaprolactam fibres
contain a higher proportion of free amino groups Ranges of acid dyes for
nylon are classified by the makiers so that users may select dyes with
good leveling or good wet-fastness properties according to their
requirements, there are also ranges with intermediate properties and
others specially designed for fabric printing.
57
Polyester Fibres:
In the course of the exploratory work that led to the development
of nylon W.H. Carothers examined aliphatic polyesters but abandoned
them in favour of the more promising polyamides. Subsequently,
however, the late J.R. Whinfield and J.T. Dickson of The Calico Printers’
Association re-examined polyesters for the purpose. They extended the
work to aromatic compounds and obtained a polymer with excellent
fibre-forming properties from terephthalic acid and ethyleneglycol. This
has the structure (3). The important fibre ‘Terylene’ was based on this

HO OC CO.O.H2C.CH2.O H

n
Work, and was first prepared in the laboratory in 1941. Development
and production of the fibre were carried out by ICI, and this fibre is now
manufactured under various names on a very large scale in many parts of
the world. Dimethyl terephthalate is now commonly used in place of the
free acid so that the terminal carboxlic acid group is esterified. Since n
has a value of about 80 the properties of the fibre are not greatly affected.
The ester is preferred as starting material because it is more easily
purified, and purity is essential in the manufacture of high polymers.
‘Terylene’ fibre is highly hydrophobic, withstands attack by
bacteria, moulds, months, acid and alkali, has high strength even in wet
conditions, is superior to nylon in resistance to light, can be heat-set and
has glood di-electric properties. It is largely used for manufacture of net
curtains, in blends with wool for suitings and other outerwer,k and for
many industrial purposes.
The hydrophobic nature of ‘Terylene’, its tightly packed
molecular structure and its lack of reactive groups all render it
unreceptive to dye molecules. Certain disperse dyes can be applied, but
under normal conditions adsorption is slow and only pale shades are
58
obtained. Much better penetration is obtained by dyeing at about 12oC
under pressure, and the special dyeing machinery required is now in
general use. Since diffusion is slow in conditions of normal use, dyeings
obtained in this way have good wet-fastness properties. Suitable dyes
must be selected for this process since not all will withstand the high
temperature without change of shade. Disperse dyes can also be applied
at temperatures below 100oC by the aid of ‘carriers’ added to the
dyebath. These agents are supplied under various brand names, such as
‘Tumescal’ (ICI), and usually consist of compounds such as o- or p-
hydroxydiphenyl. Their presence greatly facilitates the dyeing process,
but the mode of action is not fully understood. This process enables
dyeing to be carried out in standard machines, but it is somewhat
expensive and has disadvantages in that the carriers are often difficult to
remove completely; their presence may cause a noticeable odour and
sometimes impairment of light-fastness.
Polyester fibres can be dyed by the Thermosol process (DuPont),
which consists in padding with disperse dye and a thickening agent, then
drying and heating at 175o – 200oC for about one minute. Under such
conditions the dye is absorbed rapidly; after scouring to remove loose
colour the dyed material is finished in the usual way.

Polypropylene Fibres:
Polyethylene has many applications in the plastic industry, but its
low melting-pointrenders it unsuitable for fibre formation. Its homologure
polypropylene exists in various forms according to the disposition of the
substituent methyl groups; the isotactic polymers, in which these groups
are all attached on the same side of the main carbon chain, can be spun
and drawn into fibres. Catalysts promoting formation of isolactic
polymers were discovered by Zeigler, and the process was further
developed by Natta and others Polyproplene fibres and hydrophobic and
resist chemical attack, but they are not readily dyed. Certain disperse
dyes can be applied, but only pale and medium shades are obtainable.
Many methods have been described in the paten literature whereby the
fibre may be modified to confer affinity for acid or basic dyes. Side
chains carrying polar groups may be grafted to the main polymer chain,
or basic substances may be included in the melt from which the fibre is
spun. Much attention has been paid to a method whereby a compound of
59
a polyvalent metal such as nickel, zinc or aluminium is incorporated in
the fibre, which can then be dyed with metalisable dyes.

Polyurethane Fibres:
Several elastomeric fibres developed in America are based on
polymeric structures containing urethane (--NHCOO--) linkages. Full
details of the processes used are not available but complex cross-linked
polymers with rubber-like properties are obtained from polyesters or
polyethers containing terminal hydroxyl groups by means of a series of
reactions involving di-isocyanantes and diamines. Typical examples of
such fibres are Lycra (Du Pont) and Vyrene (U.S. Rubber Co.), which
are extensively used for foundation garments and swimsuits. These fibres
have advantages over rubber in strength, resistance to oxidation,
perspiration and cosmetic oils, also in whiteness and affinity for dyes.
They are readily dyed by acid, basic and disperse dyes, but fastness
properties are in general rather low.

Polyacrylonitrile Fibres:
The simplest, polyacrylonitrile fibres are straight polymers of

CH2-CH-

CN
n
acrylonitrile with structure where n varies from
600 to 2000. The first commercial fibre of this type was Orlon,
introduced by DuPont in 1948. It can be dyed by basic dyes or by acid
dyes in presence of copper sulphate. Various modified acrylic fibres
(often called ‘modacrylic’ fibres) are now obtained by copolymerising
acfrylonitrile with other substances, and dyeing properties are thereby
improved; Orlon as now manufactured is a copolymer, but the identity of
the second component has not been disclosed. Acrilan (Chemstrand
Corporation), Dynel (Union Carbide Corporation) and courtelle
(Courtaulds Ltd.) are other modified acrylic fibres. In general acid,
disperse, basic and vat dyes can be applied to these fibres, but acid dyes
are not recommended for Courtelle.
60
The older basic dyes often show better light fastness on acrylic
fibres than on natural fibres, but new basic dyes have been developed
with fastness properties on polyacrylonitrile that are fully compatible
with modern standards.

How do dyes stick to fibres?


This depends on the dye and the fibre to which the dye is attached.
Protein-based fibres such as wool and silk have free ionisable CO2H and
NH2 groups on the protein chains which can form an electrostatic
attraction to parts of the dye molecule. For example the sulphonate
group, SO3-, on a dye molecule can interact with a NH3+ group on the
protein chain.

Cotton is a polymer with a string of glucose units joined together. Indigo


which is used to dye denim jeans is a vat dye. Indigo is insoluble in
water. The reduced form of indigo is soluble. Cotton is soaked in a
colourless solution of the reduced form. This is then oxidised to the blue
form of Indigo which precipitates in the fibres.
Direct dyes are applied to the cotton in solution and are held to the
fibres by hydrogen bonds and instantaneous dipole-induced dipole
forces. These are weak compared with covalent bonds hence these dyes
are only fast if the molecules are long and straight.
Fibre reactive dyes actually form covalent bonds with fibre
molecules and are therefore extremely colour fast. A dye molecule is
reacted with the molecule trichlorotriazine:
61
Trichlorotriazine can react with either –OH groups (present in cotton) or
–NH groups (present in wool and nylons), thus effectively bonding the
dye to the fabric.

62
Reactive Dyes 5
A reactive dye, according to a useful definition by Rys and
Zollinger, is a coloured compound which has a suitable group enable of
forming a covalent bond between a carbon atom of a hydroxy, an amino
or a mercapto group respectively of the substrate. They point out that this
definition excludes mordant dyes and 1: 1 chromium azo dye complexes,
which are used in dyeing protein fibres, may form covalent bonds
between metal ion and nucleophilic groups of the fibre.
The idea that the establishment of a covalent bond between dye
and substrate would result in improved wash fastness compared with that
of ordinary dye-substrate systems where weaker forces were operative is
an old one. Attempts were made by various dye firm s from about 1906
onwards to achieve this aim but it was not until 1956 that the first
successful reactive dyes, the Procions, were introduced by ICI for the
dyeing and printing of cellulose fibres, following the work of Rattee and
Stephen from 1954 onwards. The invention consisted in the synthesis of
dyes containing a reactive group, the 2,4,6-dichlorotriazinylamino group
which has two labile chlorine atoms activated by the electron-
withdrawing action of the three N atoms, and the
Cl
C
H2N N

Dye N C CCl
H N
RO-
or
HO-

OR OR OH
C C C
H2N N H2N N H2N N

Dye N C COR Dye N C COH Dye N C COH


H N H N H N

R=Cellulose residue

63
Devising of dyebath conditions, which, while bringing about the
formation of a covalent bond, were mild enough to avoid serious damage
to the fibre. The dyeings were carried out at ordinary temperatures,
‘fixation’ being brought about by the addition of sodium bicarbonate,
thus raising the pH. The reaction with cellulose may be represented as
nucleophilic substitution by the attaching species RO- or HO- where R =
cellulose moiety. Attach by HO-, derived from the water of the dyebath,
occurs simultaneously, but that of cellulose onion predominates since the
dye is absorbed by the cellulose fibres and dye-substrate reaction is
therefore facilitated. It is necessary to remove hydrolysed unfixed dye by
through soaping and washing otherwise inferior fastness to wet treatment
results. An example of a Procion M dye is the following:

Cl
C
N
SO3Na
OH HN C CCl
N=N N

NaO3S SO3Na

Procion red MX-2B(ICI)


These dichlorotriazinyl dyes, being relatively easily hydrolysed,
tend to be unstable in storage.
The Swiss Company CIBA had been interested from 1930
onwards in the introduction of triazinyl groups into dye molecules and
had patented, manufactured and marketed monochlorotriazinyl dyes,
though not as reactive dyes. In 1957 ICI and CIBA jointly introduced the
Procion H and Cibacron ranges which require a higher temperature (60-
90 oC) and a higher pH to bring about fixation, but are more stable in
storage. An early example is:

64
Cl
C
N
SO3Na
OH HN C CNH2
N=N N

NaO3S SO3Na

Cibcron brilliant red B


The chlorotriazinyl reactive dyes are by far the most important class and
have proved a serious rival to the vat dyes as regards wash-fastness and
in other ways. The main chromogens employed are azo, metal-azo,
anthraquinone and phthallocyanine systems. The question of cotton
substantivity is an important one. It should be high enough to ensure a
high ‘fixation-yield’ but at the same time a substantivity of the unfixed,
hydrolysed dye should be low enough to permit easy removal by soaping
and rinsing to ensure maximum fastness to wet treatments in the finished
dyeing. Structural modifications to the molecule, which (a) inhibit
coplanarity or (b) increase the water-solubility, tend to reduce
substantivity.
Since their introduction reactive dyes have been the subject of a
very large number of patents comparable only with the numbers granted
for inventions in the disperse dye field and in that of synthetic organic
pigments. Most dye manufacturers have invested heavily in research
programmes concerning new reactive systems and variations of molecular
structure to achieve optimum fastness and other properties. Attention has
naturally turned to reactive dyes for substrates other than cellulose and dyes
have been developed which are suitable for wool and polyamides. Water-
insoluble disperse dyes having reactive groups (Procynyl dyes, ICI) have
been introduced principally for the dyeing of polyamide fibres on which
they show improved washing and heat fastness. Reactive systems may
be divided into two main types:

• Those involving nucleophilic substitution


• Those involving nucleophilic addition
65
Nucleophilic substitution systems:
The monochloro and dichlorotriazinyl dyes, of which early
examples have already been given, account for 50% of all reactive dyes
used in commerce.
The dye:
OH OH NH.Ph
N
Cl.C C .NH N=N

N N NaO3S SO3Na
C.
Cl
As the 1: 2 chromium complex, is claimed in B.P. 938 125 (ICI) to dye
cotton dark-green of excellent all round fastness. An example of a copper
phthalocyanine dichlorotriazinyl dhye is afforded by:
SO2.NMe
CuPC= (SO3H)2

SO2.NH
N
NH. C C . Cl

N N
C.
Cl
Which, according to B.P. 948 256 (ICI), dyes cotton a bright greenish-
blue of excellent fastness to wet treatments.
The blue monochlorotriazinyl dye.
O

SO3Na

HN
O
H N
NaO3S NC C OPh

N N
C.
Cl

66
B.P. 1230 722 (CGY) is said to have good light fastness and outstanding wet
fastness. Dyes stemming from sulphonyl chloride derivatives of copper
phthalocyanine by reaction with N- (β-hydroxyethyl) ethylenediamine,
followed by condensation with 2,4-dichloro-6-methoxy-3-triazine are
described in B.P. 1 227 538 (ICI).
It should be noted that improved fixation can be obtained by
introducing a second monochlorotriazinyl group into the reactive dye
molecule. Such dyes from the basis of the Procion Supra range of ICI.

Trichloropyrimidine dyes:
These are derived from tetrachloropyrimidine:
Cl
.
C4
N3 5 C.Cl

6
Cl .C 2 1 C.Cl
N
The electron-withdrawing properties of the two nitrogen atoms render
the chlorine atoms in position 2,4 and 6 labile; that in position 5 is
unreactive. The trichloropyrimidine dyes do not equal the
dichlorotriazines in reactivity and their fixation on the fibre requires
temperatures. The dyes themselves are stated to be less sensitive to
hydrolysis. Trichloropyrimidine dyes are marketed as Drimarenes
(S) and Reactones (Gy) and are the general structure.

Fluorine atoms replace chlorine atoms in other pyrimidine systems e.g.


Cl F
C C
H DRIMALAN (S)
Dye N C N VERAFIX(FBY)
LEVAFIX(FBY)
N C
F
Among other heterocyclic systems are the 2-chlorobenzthiazole system:
O
Dye NC S
H REATEX (FRAN)
C Cl
N

67
The chloropyridazine systems:

O
Dye N C Cl
H SOLIDAZOL(FRAN)
Cl N
N
O
Cl
Dye N C
H N REATEX(FRAN)
N
Cl

Quinoxaline derivatives:
The use of various qu8inoxaline derivatives is covfred by B.P. 995
796 (Fby):
N

.X
=C

C .X
N=

Where X = halogen, Y = H, Cl, Br, Qalk and other groups.


An example of a typical dye is given in B.P. 993 747 (F.By):
Cu
O O
SO3H SO3H
N=N
N
Cl.C CO.NH SO3H

SO3H SO3H
Cl.C
N

The acid chloride of the quinoxaline is condensed with the free amino
group at position 6 in the monoazo copper at 40oC and pH 6.5-7-0 under
which conditions neither chlorine atom undergoes hydrolysis. This class
of reactive dyes is marketed as the Levafix E range (Fby).

68
Chloroacetyl and bromoacetyl derivatives:
The Drimalan (S) dyes employ a – halogenoacetyl groups as
reactive centre and this group occures (along with monochlorotriazinyl
dyes) in the Cibalan Brilliant dyes (CIBA). In both cases the main
application is in wool dyeing. The principal has been applied to disperse
dyes as in B.P. 977 222 (S):
O O

NH2 NH2
Br2 in O - dichlorobenzene

NH NH
O O
CO.Me CO.CH2.Br

The resulting reactive disperse dye gives blue dyeings on polyamides of


excellent fastness to wet treatments.
Nuclear halogen, activated by electron, withdrawing groups such as –
NO2 in o- or p-positions, can also serve as a reactive centre as in:
HO3S NO2

OH N=N
NH2 NH.CO
Br
HO3S SO3H

Which is claimed in B.P. 982 583 (CFM) as giving bluish-red prints on


cotton of very good wet fastness and dischargeability.

Vinylsulphone dyes:
The Removal (FH) dyes employ the vinylsulphone group as in
Dye.SO2 CH=CH2 or compounds giving the vinyl group on treatment
with alkali, i.e. under dyeing conditions:
Dye.SO2CH2.CH2OSO3Na+NaOH►Dye.SO2CH=CH2+Na2SO4+H2O
Or
Dye SO2 CH2 Cl+NaOH ► Dye.SO2CH=CH2+Na2.Cl+H2O
. . .

The reaction mechanism leading to the formation of a covalent link with


the substrate concerns the formation of a carbonium ion, facilitated by
the electron-withdrawing properties of the sulphone group, followed by
interaction with the anionic centre in the cellulose fibres:
69
Dye.SO2–CH=CH2+O–Cellulose Dye.SO2.CH2–CH2.O–Cellulose

The mechanism is thus essentially one of nucleophilic addition. The


Cavalites (DuP) also employe the vinylsulphonyl group (and also the
chloroquinoxalines) while in the Levafix (Fby) range the
vinylsulphonamides
Dye.SO2NHCH2CH2OSO3Na
Are the relative groups, SO2NH.CH=CH2 being formed under the
conditions of dyeing or printing. The ‘dye’ portion of the molecule is a
water-insoluble pigment, the molecule of which contains no – SO3H or
other solubilizing group. It is of interest also that β-
thiosulphatoethylsulphones, ―SO2CH2CH2.S.SO3H, are converted by
bases into vinylsulphones. The Bunte sals or organic thiosulphate salts
derived from dye molecules are capable of reacting directly with the thiol
groups in wool fibres.
–SH+SCH2CONH Dye
SO3Na → –S.S.CH2CONH Dye

Acrylamide dyes:
The Primazin (BASF) dyes embody the acrylamide group –
. .
NH CO CH=CH2 or a precursor such as –NH.CO.CH2CH2OSO3Na. As with
the vinyl sulphones mechnism is primarily concerned with nucleophilic
addition. The Procilan dyes for wool (ICI) embody the acryloylamino group
attached to a 1: 2 nickel or cobalt azo complex. The Lanasol dyes (CGY)
have as reactive centre the a – bromoacryloylamino group – NHCOC=CH2.

Evidence for chemical combination


Cellulose
Stamm, zollinger and co-workers have endeavoured to obtain
experimental evidence of the formation of a covalent link and to
demonstrate its position in the D–glucose unit of cellulose. Cotton dyed
with a Remazol dye was subjected to microbiological hydrolysis, a
mixture of oligomers being formed. Further degradation, with dilute
sulphuric acid, gave a glucose derivative in which one hydroxyl group
was blocked by a dye molecule. Methylation of this under very mild
conditions, followed by alkaline treatment to remove the dye molecule,
70
and then acid hydrolysis to remove the glucosidic methyl group gave
finally a known trimethylglucose. Stamm later showed that a glucoside is
normally formed by Remazol dyes acting on cellulose and concluded that
the earlier findings were ambiguous.
Cellulose dyed with a chlorotriazinyl reactive dye however will
not dissolve in cuprammonium solution, whereas cellulose dyes with
direct dyes will dissolve.
Work on the attachment of reactive disperse dyes to polyamides
has shown that both – CO.NH – groups and terminal – NH2 – groups are
most probably involved. There is good evidence that chemical
combination does not indeed occur in that polyamides dyed with reactive
disperse dyes cannot be ‘stripped’ by solvents in contrasts to the same
substrate dyed with conventional disperse dyes or azoic combinations,
from which the colorant can be removed by solvents. Another striking
demonstration is afforded by diluting a solution of dyed polyamide in o-
chlorophenol. In the case of a reactive dye a coloured precipitate is
obtained while the aqueous phase is colourless; with conventional dyes,
coloration of the aqueous phase occurs.
It is clear from the number of published patents relating to reactive
dyes that this field is regard as being of the highest importance by the
dye-maker and dye-user. Much work is also being done on the kinetics
and physical chemistry of dyeing and printing processes in which
reactive dyes are involved; in this, as in other fields of dye technology,
progress is thereby accelerated.

71
COMMERCIAL POPULAR REACTIVE DYES
COLD DYEING BRANDS

# Commercial C.I. Constitution Remarks Hue


Generic
Name
1. Brill. Reactive Monoazo Reactive Bright Reddish
Yellow AG Yellow 4 Dichlorotriazinyl yellow
2. Yellow RG Reactive Azo Reactive Bright Reddish
Yello2w 7 System – Yellow
Dichlorotriazinyl
3. Yellow 4R Reactive Monoazo Bright Reddish
Orange 14 (Pyrazolone) Orange
4. Brill. Reactive Azo Reactive Bright Reddish
Orange 2R Orange 14 System – Orange
Dichlorotriazinyl
5. Brill. Red Reactive Monoazo Reactive Bright Blush
EB Red 2 System – Red
Dichlorotriazinyl
6. Brill. Rose Reactive Azo Reactive Bright Blush
3B Red 11 System – Red
Dichlorotriazinyl
7. Brill. Pink Reactive Azo Bright Bluish
B Red 74 Pink
8. Brill. Reactive Azo Bright Reddish
Magenta B Violet 13 Violet
9. Brill. Violet Reactive Azo Bluish Violet
RR Violet 14
10 Brill. Blue Reactive Anthraquinone Bright Blue
R Blue 4 Reactive system –
C.I.No.61 Dichlorotriazinyl
205
11. Navy Blue Reactive Azo (copper Reddish Navy
3R Blue 9 complex) Reactive
System –
Dichlorotriazinyl

72
HOT DYEING BRANDS

# Commercial C.I. Generic Constitution Remark Hue


Name Name
1. Brill. Reactive Monoazo Bright
Yellow 4G- Yellow 18 (pyrazolone) Greenish
X Monochlorotriazinyl Yellow
2. Yellow R-X Reactive Azo Bright
Yellow 46 Reddish
Yellow
3. Golden Reactive Monoazo Yellowish
Yellow IR Orange 12 Orange
4. Brill. Reactive Azo Bright
Orange R Orange 37 Reddish
Orange
5. Brill. Reactive Monoazo Reddish
Orange 2R Orange 13 Orange
6. Brill. Red Reactive Red Azo Bright
6B 76 Bluish Red
7. Brill. Red Reactive Red Azo Bright
8B 31 Bluish Red
8. Brill. Violet Reactive Azo (copper Bright Violet
3R Violet 1 complex) Reactive
system –
Monochlorotriazinyl
9. Red Brown Reactive Monoazo(Chhromi- Bordeaum
4R Brown 9 umcomplex)
10. Turquoise Reactive Phthalocyanine Greenish
Blue A Blue 71 Blue
11. Turquoise Reactive Phthalocyanine Bright
Blue 2-G-X Blue 3 Greenish
Blue
12. Turquoise Reactive Phthalocyanine Greenish
Blue 25 Blue 25 Blue
13. Navy Blue Reactive Azo Reddish
R Blue 59 Navy

73
BIFUNCTIONAL DYES (SUMITOMO CHEMICALS JAPAN)

No. Commercial Name C.I. Generic Name


1. Sumifix Supra Reactive Y-145
Yellow 3RF
2. Sumifix Supra Reactive R-194
Brill. Red 2BF
3. Sumifix Supra Reactive R-195
Brill. Red 3BF
4. Supra Navy Reactive B-194
Blue 2GF
5. Yellow FGS Reactive Y-115
6. Yellow GNS Reactive Y-115
7. Yellow GR Special Reactive Y-116
8. Brill. Scarlet R Reactive R-113
9. Brill. Red G Reactive R-112
10. Brill. Red BS Reactive R-111
11. Navy Blue GS 15% Reactive B-147
12. Turquoise Blue BF Reactive B-148

REACTIVE DYES IN PAKISTAN:


Cotton is the main crop of Pakistan so the main substrate for
textile dyeing & processing purpose is cellulose or cotton.
Cotton fabric can be dyed with a large number of dyes like vats, directs,
sulphur etc In Pakistan the main consumable dyes for cotton are Reactive
dyes. This is because of the following reasons:
1. In Pakistan a large number of reactive dyes class available.
2. It forms a co-valant linkage with cellulose so the fastness
properties achieved can satisfied the customers.
3. Can be applied both in Exhaust & Continuous process.
4. Most of the reactive dyes are economical.
5. A wide range of color is available.
6. From some of the manufacturer also available in granular form.
The main classes of reactive dyes now available in Pakistan are
discussed below:

74
SUMITOMO CHEMICALS (OSAKA, JAPAN):

BI-FUNCTIONAL DYES:
1. SUMIFIX SUPRA YELLOW 3RF
2. SUMIFIX SUPRA RED 3BF
3. SUMIFIX SUPRA BLUE BRF
4. SUMIFIX SUPRA YELLOW EXF
5. SUMIFIX SUPRA RED EXF
6. SUMIFIX SUPRA BLUE EXF
7. SUMIFIX SUPRA YELLOW 3RS
8. SUMIFIX SUPRA RED 3BS
9. SUMIFIX SUPRA NAVY BLUE BS
10. SUMIFIX SUPRA NAVY BLUE BF
11. SUMIFIX SUPRA NAVY BLUE EXF
12. SUMIFIX SUPRA RED 2GF 125%
13. SUMIFIX SUPRA RED 3GF 150%
14. SUMIFIX SUPRA NAVY BLUE 3GF
15. SUMIFIX SUPRA RED BB 150%
16. SUMIFIX SUPRA YELLOW GN 150%
17. SUMIFIX SUPRA YELLOW GR 150%
18. SUMIFIX SUPRA YELLOW GL 150%

SUMIFIX –HF DYES:

1. SUMIFIX HF YELLOW 3R
2. SUMIFIX HF RED 2B
3. SUMIFIX HF BLUE BG
4. SUMIFIX HF NAVY 2G

SUMIFIX VS DYES:

1. SUMIFIX BLUE R 150%


2. SUMIFIX TURQ BLUE G 150%
3. SUMIFIX TURQ BLUE G 225%
4. SUMIFIX BLACK A
5. SUMIFIX BLACK B 150%
6. SUMIFIX YELLOW 4GL
75
7. SUMIFIX BLACK EXF (A)
8. SUMIFIX ORANGE GRS 200%
9. SUMIFIX YELLOW 3GF 150%

KYUNG-IN SYNTHETIC CORPORATION (SEOUL, KOREA):

1. SYNOZOL BLACK HF-GR 130%


2. SYNOZOL BLACK SHF -RW 150%
3. SYNOZOL BLACK B 150%
4. SYNOZOL BLUE SHF-BRN 111150%
5. SYNOZOL BLACK HF- GR 130%
6. SYNOZOL BLUE SHF-BRS 150%
7. SYNOZOL BRILLIANT BLUE R 150%
8. SYNOZOL BRILLIANT BLUE R SPL
9. SYNOZOL BRILL BLUE R 150 % SPL
10. SYNOZOL BRILLIANT ORANGE 3R 150%
11. SYNOZOL GOLDEN YELLOW HF-2GR 150%
12. SYNOZOL GOLDEN YELLOW HF-4GR
13. SYNOZOL GOLDEN YELLOW SHF-RN 150%
14. SYNOZOL GREEN HF-GG
15. SYNOZOL NAVY BLUE HF-2GB150%
16. SYNOZOL NAVY BLUE RH 150%
17. SYNOZOL NAVY BLUE SHF-BR
18. SYNOZOL ORANGE SHF-RR
19. SYNOZOL RED HF-6BN 150%
20. SYNOZOL RED SHF-BN 150%
21. SYNOZOL RED SHF-EP CONC
22. SYNOZOL RED SHF-GD
23. SYNOZOL SCARLET SHF-2GN 150%
24. SYNOZOL TURQUOISE BLUE HF-G 165%
25. SYNOZOL VIOLET SHF-3B
26. SYNOZOL YELLOW HF-3GN
27. SYNOZOL YELLOW HF-4GL 150%

76
REFAFIX DYESTUFFS (KOREA) :

1. REFAFIX LEMON YELLOW 4GL


2. REFAFIX ORANGE 2RN
3. REFAFIX GOLDEN YELLOW 3RN
4. REFAFIX RED 3BN
5. REFAFIX TURQUOISE BLUE G 170%
6. REFAFIX NAVY BLUE BF
7. REFAFIX VIOLET 5R
8. REFAFIX BLACK B 150%
9. REFAFIX BLACK GR

P.T.SINAR (INDONESIA):

1. SINARCION RED BF 2B 150%


2. SINARCION YELLOW BF 4R 150%
3. SINARCION BLACK VBB 150%
4. SINARCION BLACK HF-GRPEX
5. SINARCION YELLOW BF 4GL 150%
6. SINARCION BLUE BFRF 150%
7. SINARCION NAVY BF2F
8. SINARCION NAVY BLUE RH
9. SINARCION ORANGE BF2B 150%
10. SINARCION RED HF
11. SINARCION YELLOW HF
12. SINARCION BLUE VR 150%
13. SINARCION BLUE VR SPL
14. SINARCION TURQUOISE BLUE VG 165%
15. SINARCION TURQUOISE BLUE GD

77
MEGHMANI DYES & INTERMIDIATES (AHMEDABAD
INDIA):

BI- FUNCTIONAL TYPE DYES:

1. REACTOBOND YELLOW ME4GL


2. REACTOBOND YELLOW 3RX
3. REACTOBOND ORANGE 2RX
4. REACTOBOND RED 3GX
5. REACTOBOND RED 2BX
6. REACTOBOND RED 2GX
7. REACTOBOND RED 3BX
8. REACTOBOND RED 3BS
9. REACTOBOND RED 6BX
10. REACTOBOND BLUE 4GX
11. REACTOBOND BLUE RB
12. REACTOBOND BLUE BFN
13. REACTOBOND NAVY BLUE 3GX
14. RECTOBOND BLUE BRX
15. REACTOBOND BLACK GR
16. REACTOBOND BLACK GF
17. REACTOBOND BLACK GRD
18. REACTOBOND BLACK GRP

HIGH EXHAUST TYPE DYESTUFFS:

1. REACTOBOND YELLOW HE6G


2. REACTOBOND YELLOW HE4G
3. REACTOBOND GOLDEN YELLOW HE4R
4. REACTOBOND ORANGE HER
5. REACTOBOND RED HE3B
6. RECTOBOND RED HE7B
7. REACTOBOND GREEN HE4B
8. REACTOBOND NAVY BLUE HER
9. REACTOBOND NAVY BLUE HE2R
10. REACTOBOND NAVY BLUE HERD
78
11. RECTOBOND NAVY BLUE HEXL
12. REACTOBOND CRIMSON HEXL
13. REACTOBOND YELLOW HEXL

VINYL SULPHONE BASED DYESTUFFS:


1. REACTOBOND YELLOW 4GL
2. REACTOBOND YELLOW FG
3. REACTOBOND YELLOW GR
4. REACTOBOND YELLOW GL
5. REACTOBOND YELLOW RNL 100%
6. REACTOBOND YELLOW RNL 150%
7. REACTOBOND GOLDEN YELLOW G
8. REACTOBOND YELLOW GN
9. REACTOBOND YELLOW RI
10. REACTOBOND YELLOW RR
11. REACTOBOND ORANGE 3R
12. REACTOBOND RED C2G
13. REACTOBOND RED 5B
14. REACTOBOND RED FBN
15. REACTOBOND RED RB
16. REACTOBOND RED 5BX
17. REACTOBOND RED BB 150%
18. REACTOBOND RED BS
19. REACTOBOND RED 3B
20. REACTOBOND RED RR
21. REACTOBOND BORDAUX B
22. REACTOBOND VIOLET 5R 140%
23. REACTOBOND VIOLET 5R 180%
24. REACTOBOND NAVY BLUE GG
25. REACTOBOND BLUE BB
26. REACTOBOND NAVY BLUE RGB 150%
27. REACTOBOND BLUE 3R
28. REACTOBOND DARK BLUE HR
29. REACTOBOND BLUE R SPL
30. REACTOBOND TURQUOISE BLUE G
31. REACTOBOND BLUE RR
79
32. REACTOBOND GREEN H6BL
33. REACTOBOND BROWN GR
34. REACTOBOND BLACK 100%
35. REACTOBOND BLACK B 150%
36. REACTOBOND BLACK RL
HOT BRAND DYESTUFFS:

1. REACTOBOND YELLOW H5G


2. REACTOBOND YELLOW H4G
3. REACTOBOND GOLDEN YELLOW HR
4. REACTOBOND ORANGE H2R
5. REACTOBOND ORANGE HG
6. REACTOBOND RED 6BX
7. REACTOBOND RED H8B
8. REACTOBOND RED PB
9. REACTOBOND RED P3BN
10. REACTOBOND RED P3B
11. REACTOBOND RED P8BN
12. REACTOBOND PURPLE P3R
13. REACTOBOND MMEGENTA PB
14. REACTOBOND BLUE P5R
15. REACTOBOND BLACK PN
16. REACTOBOND TURQUOISE BLUE H5G
17. REACTOBOND TURQUOISE BLUE HA
18. REACTOBOND BLUE P3R
19. REACTOBOND NAVY BLUE P2R
20. REACTOBOND BLACK P2R
21. REACTOBOND BLACK PGR
22. REACTOBOND BLACK XLW

COLD BRAND DYESTUFFS:

1. REACTOBOND YELLOW M8B


2. REACTOBOND YELLOW M4R
3. REACTOBOND ORANGE M2R
4. REACTOBOND RED M5B
5. REACTOBOND RED M8B
80
6. REACTOBOND MEGENTA MB
7. REACTOBOND VIOLET C4R
8. REACTOBOND BLUE MR
9. REACTOBOND BLUE M2R
10. REACTOBOND BLUE M4GD
REACTOBOND XL DYES:

1. REACTOBOND YELLOW XL
2. REACTOBOND RED XL
3. REACTOBOND RED XL3B
4. REACTOBOND BLUE XL
5. REACTOBOND NAVY BLUE XL
6. REACTOBOND BLACK XL

REACTOBOND HEXL DYES:

1. REACTOBOND YELLOW HEXL


2. REACTOBOND CARAMINE HEXL
3. REACTOBOND CRIMSON HEXL
4. REACTOBOND RED HEXL
5. REACTOBOND NAVY BLUE HEXL

JAY CHEMICALS INDIA:


1. JAKAZOL BLACK B 150%
2. JAKAZOL BLACK GG
3. JAKAZOL BLACK GR CONC
4. JAKAZOL BLACK HF-GR
5. JAKAZOL BLACK HFGRPEX
6. JAKAZOL BLACK SJ
7. JAKAZOL BLUE JRF
8. JAKAZOL BLUE ME2RL
9. JAKAZOL BRILL BLUE R SPL
10. JAKAZOL BRILL RED RB 133%
11. JAKAZOL GOLDEN YELLOW MERL 150%
12. JAKAZOL GOLDEN YELLOW RNL 150%
13. JAKAZOL GREEN ME4BL
81
14. JAKAZOL GREY MEN BF
15. JAKAZOL GREY MER VS
16. JAKAZOL NAVY BLUE ME2GL
17. JAKAZOL BLUE ME-BF
18. JAKAZOL NAVY BLUE ME-GFN
19. JAKAZOL ORANGE 3R
20. JAKAZOL ORANGE ME2RL
21. JAKAZOL RED ME4BL
22. JAKAZOL RED MEGF
23. JAKAZOL TURQ BLUE GD SPL
24. JAKAZOL TURQ BLUE PG
25. JAKAZOL VIOLET 5R
26. JAKAZOL VIOLET ME –B2
27. JAKAZOL YELLOW FG
28. JAKAZOL YELLOW GR
29. JAKAZOL YELLOW 4GL

DYESTAR (GERMANY)
REMAZOL
1. GOLDEN YELLOW RGB
2. GOLDEN YELLOW RNL GRAIN 150%
3. RED RB GRAIN 133%
4. TURQ BLUE G 133%
5. BLACK B GRAIN 133%
6. DEEP BLACK N GRAIN 150%
7. BRILLIANT BLUE R SPL
8. YELLOW 3RS GRAIN 133%
9. NAVY GG GRAIN 133%
10. NAVY RGB GRAIN 150%
11. BRILLIANT BLUE RN GRAIN
12. BRILLIANT ORANGE 3R GRAIN
13. BRILLIANT RED 3BS GRAIN
14. BRILL VIOLET 5R
15. BRILL YELLOW GL GRAIN
16. RED RGB
17. DEEP RED RGB
18. YELLOW 3RS-A 150%
82
19. BRILL RED 3BS-A 150%
20. BLACK GSA

LEVAFIX:

1. ORANGE E3GA
2. BRILL RED E4BA GRAIN
3. BRILL YELLOW E3G GRAIN
4. YELLOW CA GRAIN
5. RED CA GRAIN
6. BLUE CA GRAIN
7. NAVY CA GRAIN
8. RUBINE CA GRAIN

SUNFIX (CHEMDYES CORPORATION)

1. SUNFIX RED S3B 150%


2. SUNFIX'YELLOWS3R 150%
3. SUNFIX RED SPD 150%
4. SUNFIX YELLOW SPD 150%
5. SUN FIX N.BI.UE SPD (SPL) 150%
6. SUN FIX BLUE SBR
7. SUN FIX RED SG (For pale shade)
8. SUN FIX. YELLOW SPR (For pale shade)
9. SUNFIX ORANGE S2R 150%
10. SUNFIX NAVY BLUE 150%
11. SUNFIX N/BLUE SB
12. SUNFIX YelJLDW S4GL 150%
13. SUNZOL BLACK B 150%
14. SUNZOL BLACK GR CONC
15. SUNZOL BIACK WN CONC
16. SUNZOL TURQ BLUE G 165%
17. SUNZOL BRILL BLUE-R (SPL)
18. SUNZOL ORANGE 3R (0RANGE-16)
19. SUNZOL VIOLET SR (VIOLET-5)
83
20. SUNZOL BLUE BB (B-220)
21. SUNZOL GREEN GG
22. SUNZOL NAVY BLUE GG
23. SUNZOL YEIJLOW 2RN(SAME AS RAMAZOL YRNL)
24. SUNZOL RED RB
25. SUNZOL REDBB
26. SUNFIX YELLOW SS
27. SUNFIX RED SS
28. SUNZOL BLACK El3 (CONC)
29. SUNZOL NAVY BLUE GRH

EVERZOL DYES (TAIWAN)


LX – DYES:
1. EVERZOL YELLOW LX
2. EVERZOL RED LX
3. EVERZOL BLUE LX

EVERZOL ED-RANGE :

1. EVERZOL YELLOW ED
2. EVERZOL YELLOW EDR
3. EVERZOL YELLOW ED-2G
4. EVERZOL RED ED
5. EVERZOL RED ED 2B
6. EVERZOL RED ED-3B
7. EVERZOL BLUE ED
8. EVERZOL BLUE ED-G
9. EVERZOL NAVY ED
10. EVERZOL BLACK ED
11. EVERZOL BLACK ED-2R
12. EVERZOL RUBINE ED
13. EVERZOL ORANGE ED-2R

84
EVRZOL BF/VS DYES:

1. EVERZOL BRILL RED F2B


2. EVERZOL BRILL. RED F3B
3. EVERZOL RED BS
4. EVERZOL BRILL RED 3BS H/C
5. EVERZOL RED RBN
6. EVERZOL RED BB
7. EVERZOL RED LF-2B
8. EVERZOL BLUE 3BR H/C
9. EVERZOL BLUE BB 133%
10. EVERZOL BLUE BRF 150%
11. EVRRZOL BRILL BLUE R S/P
12. EVERZOL BRILL BLUE R S/P H/C
13. EVERZOL TURQ. BLUE G
14. EVERZOL TURQ. BLUE VSG 133%
15. EVERZOL G. YELLOW 3RS H/C
16. EVERZOL L.YELLOW 3GL
17. EVERZOL BRILL YELLOW 4GL
18. EVERZOL YELLOW GR
19. EVERZOL YELLOW F3R H/C
20. EVERZOL G. YELLOW RNL
21. EVERZOL YELLOW PEG
22. EVERZOL NAVY BLUE BDF
23. EVERZOL NAVY BLUE GG
24. EVERZOL NAVY BLUE FBN
25. EVERZOL NAVY BLUE RGB
26. EVERZOL NAVY BLUE RGB H/C 150%
27. EVERZOL BRILL ORANGE 3R
28. EVERZOL BLACK B H/C
29. EVERZOL BLACK CRN
30. EVERZOL BLACK GSP
31. EVERZOL BLACK N
32. EVERZOL BLACK NR
33. EVERZOL BLACK GR
34. EVERZOL BLACK MW
35. EVERZOL BLACK GRB
85
36. EVERZOL ORANGE ED-2R

NEW RANGE:

1. EVERZOL YELLOW 2GR 150%


2. EVERZOL RED 6BN 150%
3. EVERZOL BLACK BFV
CLARIENT SWITZERLAND DYES

K-DYES :
1. DRIMEREN RED K4BL
2. DRIMEREN BLUE K2RL
3. DRIMEREN TURQ BLUE K2B
4. DRIMEREN NAVY KGRL
5. DRIMEREN GOLDEN YELLOW K2RL
6. DRIMEREN ORANGE KGL
7. DRIMEREN ORANGE K3R
8. DRIMEREN ORANGE KR
9. DRIMEREN VIOLET K2R
10. DRIMEREN BLACK K3B
11. DRIMEREN YELLOW K2GLK 200%
12. DRIMEREN GREEN K5BL

CL-DYES:
1. REACTIVE YELLOW CL3G
2. REACTIVE YELLOW CL2R
3. REACTIVE ORANGE CL3B
4. REACTIVE RED CL5B
5. REACTIVE CL3BL
6. REACTIVE BLUE CLRL
7. REACTIVE TURQ BLUE CLB
8. REACTIVE BLUE CLR

86
Direct Dyes 6
The direct dyes, also known as the substantive colours, differ from
the basic and acid dyes because cellulosic fibres have a strong affinity for
them. Many of them will also dye the protein fibres and, as was
explained in the previous chapter, the majority is sulphonated azo
compounds very similar to the acid dyes in constitution, there being no
clear demarcation between the two classes. Selected substantive dyes can
be used to give solid shades on wool and cotton mixtures.
This was the first direct dye, and its discovery was quickly
followed by the preparation of many similar colours, opening a new era
in cotton dyeing. Before 1884 cellulosic fibres could only be dyed on a
mordant or by means of indigo and a limited number of other naturally
occurring vat dyes. Both of these methods were troublesome and
expensive. Cotton was made in large quantities in the last century for
markets where cheapness was a most important consideration. The direct
dyes were inexpensive and easy to apply and, although of indifferent
wet-fastness, their use spread with great rapidity because they fulfilled an
outstanding demand. New members with improved fastness are still
being added to this class.

Chemical constitution of direct dyes:


Most of the colours belonging to this class are sulphonated azo
compounds. A simple monazo direct dye is Diazamine Scarlet B (C.I.
Direct Red 118), formula (1):
N N (1)
SO3Na NH.CO NH2

and the original Congo red (C.I.Direct red 28) formula 2


NH2 (2)
NH2 N N
N N

SO3Na NaO3S
87
Was a bisazo compound prepared by coupling benzidine diazotized at
both amino groups with 2 molecules of naphthionic acid Diazo Brown
3RNA.CF (C.I. DIRECT BROWN 138), formula (3)
NH2 NH2
NH2

H2 N N N N N N N NH2

SO3Na
is a trisazo direct dye of comparatively simple structure and a polyazo or
tetrakis azo member of the class is Chlorazol Brown GM (C.I. DIRECT
BROWN 44), formula (4)

NaO3S N=N- N=N- N=N- N=N- SO3Na


NH2 NH2

An important group of the direct dyes is those derived from stilbene,


formula (5), such as Diphenyl Chrysoine G (C.I. DIRECT YELLOW
19), formula (6)
NaO3S

CH N=N- OH
CH

CH CH N=N- OH

NaO3S
(5) (6)
In 1887 Green prepared Primuline, formula (7), which was the fast of the
Thiazole direct dyes.
NaO3S

S
CH3 S NH2
C C

N
N

(7)
88
CLASSIFICATION ACCORDING TO DYEING BEHAVIOUR

It was appreciated by earlier workers that the behaviour of


individual direct dyes varied considerably. This necessitated special care
in selection, particularly in mixture, in order to achieve optimum results
and to prevent the occurrence of faults, such as uneven or insufficiently
penetrated dyeings on all types of materials and listing or ending with
jig-dyed fabrics. As a result attention was given to devising suitable
laboratory test methods to characterise the dyeing behaviour of
individual direct dyes and thereby enable the best selection to be made
for a particular dyeing method, highlighting the parameters to be
observed in controlling the dyeing cycle.
In the UK pioneer work in this area by C M Whittaker, John
Boulton and their colleagues at Courtaulds in the 1940s was concerned
with the dhyeing of viscose. A characteristic of individual direct dyes,
described as the time of half dyeing (i.e. the time taken to reach 50% of
the equilibrium absorption under specified conditions), is an indication of
the rate at which a direct dye is absorbed by the fibre. In the direct dye
range it varies from 0.72 to 280 min. Arising from this work, it was
suggested that dyes exhibiting a similar time of half dyeing would be the
preferred choice in mixtures. It was found later, however, that
measurements of the so-called rate of dyeing, related to time of half
dyeing, were inadequate to obtain a full understanding of the
compatibility of direct dyes. Subsequently it was confirmed that rate of
dyeing alone is insufficient to predict compatibility and that rate of
migration and salt controllability are of greater importance.
As a result of a detailed study of the subject by the Society of
Dyers and Colourists’ Committee on the Dyeing Properties of Direct
Cotton Dyes it was concluded that determination of four parameters was
necessary, i.e., migration (or leveling power), salt controllability and the
influence of temperature and of liquor ratio on exhaustion. Tests are
prescribed for migration and salt controllability whilst a statement covers
the influence of temperature and liquor ratio, no tests being prescribed.
The aforementioned SDC committee recommended that direct dyes be
classified as follows.

89
Class A
Dyes, which are self-levelling, i.e. dyes of good migration or
leveling properties.
Class B
Dyes which are not self-levelling, but which can be controlled by
addition of salt to give level results; they are described as salt
controllable.
Class C
Dyes which are not self-levelling and which are highly sensitive to
salt; the exhaustion of these dyes cannot adequately be controlled
by addition of salt alone and they require additonal control by
temperature; they are described as temperature controllable.

Widespread use is made of the SDC ABC classification and it is


included in many dye manufacturers’ pattern cards and other technical
literature. A typical dye maker’s range of direct dyes would contain
roughly 20% class A, 40% class B and 40% class C dyes.
The prescribed tests were based on the use of unmercerised cotton
and were found subsequently to be equally applicable to mercerised
cotton, viscose and linen.
Amplification and some modifications of the SDC ABC
classification were undertaken by Beal and the results were given in the
form of graphs covering gthe following factors: rate of exhaustion and
degree of migration (which are characteristics properties of individual
dyes), time and temperature of dyeing, electrolyte concentration and
liquor ratio (all the last four being external factors capable of control);
these graphs are now seldom used. A study of the migration properties
of direct dyes was made by Cegarra to ascertain the effect of variations
in temperature, electrolyte concentration, liquor ratio and agitation of the
dye liquor. It was found that at low temperature an increase in
temperature improved migration more effectively with classes A and B
dyes than with class C direct dyes. An optimum electrolyte concentration
for maximum migration is shown by classes A and B dyes but with class
C dyes that migration diminishes steadily as the electrolyte concentration
is increased. Increase in liquor ratio increases migration of classes B and
C but not that of class A dyes. Agitation increases migration of all three
classes of yes.
90
Temperature-ranges tests are useful for determining the behaviour
of individual dyes at various temperatures of dyeing and are of particular
value in the selection of compatible dyes for mixtures. The percentage
absorption of dye under standard conditions of electrolyte concentration,
liquor ratio and time of dyeing at a variety of temperatures is estimated
visually or colorimetrically and the results are given in the form of
graphs.
The selection of compatible dyes for padding and jig dyeing
processes is not whooly covered by the SDC ABC classification and
related tests. This can be done, however, by carrying out simple dip or
strike tests in which fabric or yarn samples are dyed for short periods,
e.g. for 1-2 min, removed from the dyebaths, replaced by fresh samples
and the procedure repeated several times; the patterns are mounted in
series and assessed visually for change of hue and depth. Marked
changes of hue indicate incompatibility.
The various tests described are simple to perform, required the
minimum of apparatus and skill, and the results obtained are easy to
interpret. They provide valuable information on the performance of
individual direct dyes, either alone or mixtures.

91
Disperse Dyes 7
Disperse dyes include water insoluble dyes which could applied
on synthetic fibres. The first disperse dyes were reported for cellulose
acetate rayon by British Celanese Corpn. in 1920. None of the other
classes of dyes had been good for dyeing cellulose acetate.
Some dyes were reported which did not possess the solubilizing
groups like SO3Na. These had been found to dye the cellulose acetate
from a water dispersion. Green and Sanders in 1923 prepared
temporarily solubilized dyes having –N–CH2SO3Na groups. These dyes
were sold as ionamines e.g., ionamine orange CB
C2H5
O2N N=N N
CH2SO3Na
This dye got hydrolysed in the dye-bath giving a finely divided
insoluble dye, which got dissolved in the fibre yielding a solid-sold
solution. These dyes lost the solubilising CH2SO3Na group on
hydrolysis. Several ionamine dyes had been marketed.
These dyes were later replaced by acetate dyes which were
aqueous disperse ions of insoluble dyes in a finely divided state (I to 4 u)
and could be able to dye the fibre from aqueous dispersion.
Several dye manufacturers produced these dyes, which were
named, disperse dyes by C.M. Whittaker in 1953. These dyes had been
dispersed by several techniques such as precipitation, milling with
surface-active agent, or milling with special kind of sand or glass. The
disperse dyes should possess a slight solubility in water for proper
dyeing. Dispersing agents are added to the dye to disallow aggregation
but to enhance solubility. Several kinds of dispersing agents like alkyl
sulphates, alkylaryl sulphonates. Fatty alcohol or amine+ethylene oxide
condensation products, naphthalene sulphonic acid+formaldehyde
condensation products, lignin sulphonate, etc. have been used with
disperse dyes.
92
Some of these dyes get sublimed during ironing. Hence a
sublimation fastness rating has to be introduced. Some of these dyes with
NH2, N-alkyl group are influenced by traces of nitrogen oxides in the
city atmosphere resulting in change of shade. Fastness to burnt gas
fumes provides rating of this capacity.
With the introduction of polyester fibres in 1950 there occurs the
rapid development in this field to make dyes suitable for polyester fibres
and several modifications have been carried out.
The dyeing could be carried out at about 100oC in presence of
emulsified aromatic compounds like biphenyl, o-phenylphenol, di and tri
chlorobenzene etc. The dyeing could be carried out of 130o in pressure
vessels. Some new methods evolved are thermofixation, solvent dyeing
and transfer printing. The chemical constitution of many of the disperse
dyes is unknown. However, most of the disperse dyes belong to azo and
anthraquine one class which will be described in the following pages.

Azo Dyes:
The monoazo disperse dyes have been reported to give almost a
complete range of shades. These dyes are largely used for cellulose
acetate (CA) and polyester (PE) fibres and their blends with cotton,
polyamides (PA), polyacrylonitriles (PAN) and cellulose triacetate
(CTA).
The CA dyes were mostly dyed red and yellow shades. They possess
simple structures e.g. cibacet yellow GBA, C.I. disperse yellow 3, 11855.
HO

H3CCOHN N=N

CH3

CI disperse red 1,11110 possesses following structure:

C2H5
O2N N=N N
C2H4OH
93
This dye is having lightfastness 5 but possesses poor sublimation
fastness. Its chloro derivative possesses higher light fastness.
Cibacet diazo black B disperse black 2, 11255 is having following
structure. It is applied to CA, then diazotised on the fibre coupled with 2,
3 hydroxy naphthaote to yield a good black:
H3C

H2N N=N NH2

OCH3
Manhy of these dyes are obtained from 4-aminophenylazobenzene
substituted in various positions. The substitution of Br, Cl, NO2 and CN
provides bathochromic shift i.e., the colour of dye moves from red to
blue end of spectrum. It is possible to intensify colours by substitution
on the nucleus as well as on the nitrogen. In the following example
substitution of R1, R2 and R3 by electron withdrawing groups causes
batho-chromic shift:
R3
C2H5

R2 N=N N

C2H4OCOC2H5
R1

The dye BP 1351382 has been a bluish green dye for PE. Its structure is
as follows:
NO2 OCH3

N=N N
S
H3CCO C2H6OCOC2H6

H3CCOHN

94
Another example of blue dye for PE is RP 1370034 whose structure is as
follows:
CN

CH3CH2OCH3

O2N N=N N

CH3CH2OCH3
BrH3CCOHN

For polyester fibres most of the cellulose acetate dyes could not be used
due to poor fastness to sublimation. As the PE dyes are fixed at high
temperatures, these dyes get sublimed to a large extent. Structural
variations are being made to make more complex dye molecules having
improved fastness for PE fibres. The following example provides the
structure of a dye molecule and effect of some substitutents of fastness
properties:
CH2CH2R1

O2N N=N N

CH2CH2R2
Cl

R1= H H OH OCOCH3 CN

R2 = OH H CN CN CN
Light
fastness 3 3.5 4.5 7 7
thermo
fixation 2.5 1.5 4 4 4.5
fastness

The cyanoethyl group tends to improve both light and thermo fixation
fastness properties. The sublimation fastness has been improved by
introducing acetylamino group in 3-position of coupling component.
The disazo dyes find use in dyeing CTA and PE fibres. The
following examples are from patents BP 1171803 Orange PE, and B.P.
1805326 Navy, P. E.

95
N=N N=N-C-C-CH3

CN

B.P.1171803 ORANGE PE OH

OCH3

C2H4OCOCH3
NO2 N=N N=N N
C2H4OCOCH3
Cl OCH3
NHSO3CH3

B.P.1805326 NAVY PE

Anthraquinone Disperse Dyes:


This group largely provides blue and violet dyes. The earliest
known dye was Duranol Red 2B, C.I. Disperse Red 1560710. Another
dye has been cellition Fast Pinki FF 3B, C.I. Disperse Red 11,
O NH2 O NH2

OCH3

O HO O NH2
DURANOL RED 2B
CELLITON FAST PINK FF 3B

The 1, 4-diaminoathraquinone dyes provide red shades on CA. By the


introduction of electron withdrawing groups it becomes possible to
improve fastness by inhibition of nitrosation or diazotisation of amino
group by nitrogen oxides. Cibacet Brilliant Blue BG C. I. Disperse Blue
361505 has been an important dye for CA, which is prepared from
leucoquinizarin by condensing with a mixture of methylamine and 2-
hydroxy ethylamine.
96
NHCH3
O O NH2

OCH3

O O
NHCH3CH2OH N

H CH2CH2OH

Disperse Blue 7 62500 is as follows:


OH NHCH3CH2OH
O

O NHCH3CH2OH
OH
1, 3, 5, 8-tetra anthraquinone is also a CA dye Disperse Blue 1 60710.
This 4-amino dye on partial methylation with methanol and sulphuric
acid provides Celliton Blue Extra C. I. Disperse Blue 31.
Many other anthraquinone dyes for PE fibres have been developed. For
example, F.P. 1345377.
H
H2N O O

OR

R=H , ALKYL
NH2 or COCH3
O O

O NH2
C=X
X=O or NH
N-R
R= ALKYLE,ALKYL ARYL
HYDROXY ALKYLE or cyano
C=X alkyle group
O NH2

97
By introducing phenoxy and other derivatives in 2-position of 1-amino 4-
hydroxyanthraquinone, it becomes possible to improve thermofixation
fastness.
O NH2

R could be O OH

O O
H

OH
OCH2CH2OCH3

O O O Cl

O SO3NHCH2CH2OC2H5
O SCH3 ,

Miscellaneous Disperse Dyes:


Nitro dyes find use of CA and PE fibres. The structure of Serilene
golden yellow RFS is as follows:
NO2 NH N=N OH

NO2

The following structure gives a nitro dye for PE having good


fastness properties according to BP 998918.
NO2

CH2CH2CH3
NH SO2 N
CH2CH2CH3

98
Methine or Styryl Dyes:
Methine dyes provide yellow shades e.g., Celliton Fast Yellow 76,
C.I. Disperse Yellow 31, 48000. It has excellent fastness properties. It is
obtained by condensing 4-(N-n-butyl-N-chloroethyl amino)-benzaldehyde
with ethylcyanoacetate.

COOC2H5 COOC2H5
C2H4Cl C2H4Cl
N CHO+CH2CN N CH=C-CN

n-H9C4 n-H9C4

Quinphthalone dyes: These are used for PE providing yellow shades.


Cl
O
OH
Cl
C

HC
N
C
Cl
O
Cl

SO2C6H5

OH O
C

N
C

O
Naphthostyril dyes provide yellow orange shades. They are obtained
from naphtho-styril by condensing with aniline derivatives e.g.,

99
HN CO

+ H2N NO2 POCl2

HN C N NO2

Coumarin Dyes:
These dyes are used for polyester fibres and give flurescent yellow
shade. A dye is obtained by condensing N, N-diethylamino-2-hydroxy-
benzaldehyde and 2-cyanomethyl benzothiazole in a mixture of acetic
acid and dimethy formamide.
CHO N
24 HOURS
+ H2C-C
C2H5 25 C
S
OH NC
N
C2H5
N

C5H2
S
N NH
C5H2

FORMAZINE DYES
These give blue disperse dyes which are suitable for nylon

O O

Ni

N C

N N
C
Benzene ring has substituents such as
CN NHCOCH3,SO2R,SO2NR1,R2
100
Vat Dyes 8
The term vat dyes relates to dyes of any chemical class that are
applied by the vat process. The dyes are insoluble in water and cannot be
used directly for dyeing, but on reduction to a leuco form they become
soluble in presence of an alkali and acquire affinity for cellulosic fibres;
a solution of a leuco compound can be applied by dyeing or printing and
on reoxidation (usually be exposure to air) the original insoluble dye is
formed witghin the structure of the fibre. A final treatment with hot soap
or other detergent brings about aggregation or crystallization so that the
particles of pigment become firmly fixed and the shade is fully
developed.
One of the earliest vat dyes was indigo, which has been used in
India from time immemorial. Another was Tyrian purple, obtained in
Mediterranean countries from certain shell-fish, and known at the time of
Moses. It may be conjectured that the vat process was developed as a
result of observation of the effect of accidental fermentation on these
natural dyes, the colour being destroyed by reduction during the process
but restored on exposure to air. The name leuco compound (Greek ------
White) is somewhat misleading, since although indigoid reduction
products are usually colourless they are applied as sodium salts which
are yellow, and in the anthraquinone series the reduction products are
coloured (but usually differing in hue from the oxidised dyes). All vat
dyes contain a quinonoid system based on carbonyl groups, and in the
vatting operation these are reduced to C-OH; since an alkaline
medium is used salts of the type C- O Na are formed. On reduction
anthraquinone forms a series of products, and vat dyes containing several
anthraquinone residuces give rise to still more complex series. In the
preparation of a vat reduction proceeds only to the hydroquinone stage,
and in complex dyes it may be unnecessary to reduce all of the keto
groups present.
All vat dyes can be applied to cellulosic fibres, and some of them
also to wool, silk, nylon and acetate fibres. The need for alkaline
101
application restricts their use on wool and acetate fibres, and in the case
of many anthraquinjone dyes the necessary conditions are unduly severe.
Protective agents such as glue are customarily used to minimise damage
to wool. Most vat dyes have low affinity for nylon, and on that fibre their
fastness to light is often lower than on wool. Dye of high molecular
weight cannot usually be applied satisfactorily to acetate fibre. Air
oxidation of leuco compounds is sometimes augmented by the used of
acid dichromate, especially if the goods are in the form of loose cotton,
cops, cheeses or pieces dyed on a ‘jigger’, when access of air is
restricted. An aftertreatment with soap or another detergent is necessary
for removal of loose pigment and promotion of crystallinity; it often
results in a marked change in shade and improvement in fastness
properties.
Some important vat dyes representing the chief chemical classes
will now be described.

Indigoid Dyes:
Indigo
Many plants of the genus Indigofera have been cultivated for
production of indigo in India, China, Japan, Central America, West
Indies, Brazil, South and Central Africa, Madagascar, Java and the
Philippine Islands. The colouring principle is present as a glucoside of
indoxyl known as indican, and this was hydrolysed to free indoxyl by
enzyme action; indigo (also known as indigotin) was obtained by
oxidation of indoxyl:
O H
O
C C N
CH2 + O2 C=C + 2 H2O
N C
N O
H H

INDOXYL INDIGO

Natural indigo contains a red isomer of indigo known as indirubin and


other impurities in varying proportions. These constituents facilitate
preparation of the vat, and were considered to have a desirable effect on
the dyed shade, but the variable properties were a nuisance to the dyer.
Woad, which was extracted from the plant Isatis tinctoria, and used in
Western Europe over many centuries for colouring yarns, fabrics and the
bodies of the inhabitants, contains a small amount of indigo.
102
After many years’ work Adolf Baeyer determined the structure of
indigo in 1883. The ethylene linkage in its molecules leads to the
possibility of stereoisomerism. It has been shown by X-ray
crystallography that indigo normally exist in the trans form, but both cis
rapidly reverts to the trans forms have been isolated; the cis rapidly
reverts to the trans form during storage hower.
Early processes for manufacturing synthetic indigo were devised
by Baeyer, Sandmeyer and Heumann, but the first commercially
successful operation was achieved by BASF in 1897 using a process
based on the fusion of o-carboxyphenylaglycine with caustic potash and
oxidation of the resulting indioxyl. In 1901 it was found by the Deustshe
Gold-un Silber-Scheideanstalt that good yield are obtained at a lower
temperature by using a fusion mixture containing sodamide, caustic
potash and caustic soda. Originally phenylglycine was obtained by
condensing aniline with chloroacetic acid, but in consequence of
shortage of acetic acid during World War I another route was introduced,
and it is still generally preferred. The whole process is represented as
follows:
CH2O+ NaCN
NHCH2CN
NHCH2SO2Na
NH2 NaHSO3

NaOH +H2O

O
C fusion with

CH2
NaNH2 + NaOH+KOH NHCH2COONa + NH3
N
H

OXIDATION

O H
C N
C= C
N C
H O

INDIGO

After the introduction of synthetic indigo, cultivation of the natural


product declined rapidloy and is now negligible. The synthetic product
103
was produced in vast quantities for many years and is still extensively
used, but it has lost much of its former importance.
For application of indigo to cellulosic fibres vats of various types
have been used. The hydrosulphite process is now the most important,
and the others (zinc-lime, ferrous sulphate, bisulphite-zinc-lime and the
traditional fermentation process) are chiefly of historical interest. The
hydrosulphite process has advantages over the others in simplicity, speed
and ease of control. It depends on the use of sodium hydrosulphite
(Na2S2O4) in conjunction with caustic soda. Indigo is easily reduced at
room temperature, giving a yellow alkaline solution of the leuco
compound. Cellulosic materials are treated in the resulting vat either cold
or at about 50o C, salt being added to improve exhaustion. Since the
leuco compound has low affinity for cellulose several impregnations
(each followed by air oxidation) may be needed for deep shades. The
dyed material is rinsed, treated with acid, rinsed again, then soaped at the
boil. The dyed shade is often modified by ‘bottoming’ or ‘topping with
dyes of other application classes.
Indigo is applied to wool by a broadly similar process, using
mildly alkaline conditions with an addition of glue or other suitable
colloid to protect the fibre. Since the affinity of reduced indigo is low
wool is usually dyed at 40o – 60o C. Several makes have marketed ready-
reduced indigo, which can be applied to wool from a bath containing
ammonia and glue.
Many textile-printing processes are available for application of
indigo to natural or synthetic fibres by means of direct, discharge or
resist styles.
Attempts to simplify the applicaltion of indigo were made by
several workers, and these culminated in the introduction of stable
disulphuric ester of leuco indigo by Bader and Sunder in 1921. This
product, having the structure, was placed on the marked by Durand and
Huguenin
OSO3Na

H
C N
C-C
N C
H

NaO3SO
104
under the name Indigosol O; equivalents are now made by many other
firms and sold under different names. Indigosol O was originally
obtained by treating leuco indigo in pyridine solution with
chlorosulphonic acid, and converting the disulphuric ester into its
disodium salt. An improved process was later discovered by Morton
Sundour Fabrics Ltd., whereby unreduced vat dyues, including indigo
and its derivatives, are treated with sulphur trioxide, chlorosulphonic
acid or methyl chlorosulphonate in presence of pyridine and a metal such
as copper, iron or zinc; an intermediate compound of the type

C OSO3 Cu.C5H5N

is formed, and on reaction with caustic soda the disodium salt of the
disulphuric Easter is obtained.
Indigosol O is readily soluble in water, has affinity for cellulose
and can be rapidly and quantitatively oxidised on the fibre with
formation of indigo. Since the affinity is somewhat low and the cost
relatively high this product is used mainly for pale shades; it is also
especially suitable for wool since it has good affinity for that fibre and
can be applied from a weakly acid bath. Development of dyed cellulose
or wool is carried out either by means of sodium nitrite (often added to
the dyebath) followed by acid treatment, or by an aftertreatment with
acid dichromate. Indigosol O can be applied to acetate fibre from a
strongly acid bath and developed by the nitrite method.
Although indigo has only moderately good fastness to light
(approximately grade 4 on cotton, or 4–5 on wool) it has a great
advantage over many other dyes in that as fading proceeds there is little
or no change in hue.

105
Thioindigoid Dyes:
Thioindigoid dye is analogues of indigo and its derivatives in
which the two – NH – groups are replaced by sulphur atoms. The first of
these, Thioindigo Red, was discovered by Friedlander in 1906.
C S
C=C
S C
O
As indicated by its name, this dye gives bluish red shades. Derivatives
with a very much wider range of shades than those available in the
indigoid series can be obtained by suitable substitution. The effect of
substituents may be either hypsochromic or bathochromic, and examples
quoted later included dyes giving orange, red, violet and brown shades.
The dyes have good fasgtness properties, and on account of their
versatility they have surpassed those of the indigoid class (except indigo
itself) in importnce. It will be seen from the following account of their
manufacture, however, that the processes required are somewhat
complex, and the resulting high cost has caused these dyes to lose favour
as cheaper products with comparable fastness properties have been
introduced.
It is not practicable to include a full account of the chemistry of
the thioindigoid dyes here, but the following examples illustrate two of
the more important industrial processes.
Example of such dyes is illustrated below. CI Vat Blue 8 (CI
73800) gives blue or heavy shades, and is applied to cellulosic fibres, silk
and wool.
Me

O O
C Cl

=C

N
H
OMe

CI VAT BLUE 8
106
CI Vat Red 45 (CI 738690) gives bright scarlet shades, and is applied to
cellulosic fibres, also to wool.

O
C
C =C
S

CO

CI VAT RED 45
Indanthren Printing Black B (FH) (CI Vat Black 2; CI 73830) is
manufactured by a condensation of a different type. Isatin a-anilide
reacts with 4-hydroxy-10-methylbenzo [a ] carbazole in presence of
acetic anhydride and formic acid with elimination of aniline to yield the
dye with structure (98). It is applied to cellulosic fibres by printing
processes to give bluish gray or bluish black shades. This dye is of little
interest for application by dyeing methods.

N O O
C
H
Me C
N
H

Anthraquinone Vat Dyes:


Over 200 anthraquinone vat dyes are at present in commercial use,
and the constitutions of about 130 of them have been disclosed. They
represent a wide variety of chemical types, and provide shades ranging
from yellow to black. Many of the dyes are very complex, and their
structures may contain up to nineteen condensed rings. They are often
107
built up by means of reactions between components containing several
reactive positions, and in consequence some of the commercial products
are mixtures.
Anthraquinone vat dyes are chiefly important in application to
cellulosic fibres by dyeing and printing processes. The conditions used
for vatting very considerably but the only reducing agent to practical
importance is alkaline sodium hydrosulphite.
The first anthraquinone vat dye was obtained by R. Bohn in 1901
in the course of an attempt to prepare an analogue of indigo by caustic
fusion of 2-anthraquinonylglycine. The expected reaction did not take
place, but a blue vat dye was formed which proved to have the structure.
The same product was obtained by caustic fusion of 2-aminoanthraquinone.
Bohn called his product

O
NH

NH O

Indanthren (the name being derived from Indigo and anthracene), and
later it was marketed by BASF as Indanthren Blue R. It will be seen that
the dye is a dihydrodianthraquinlonylazine, and it was later given the
chemical name indanthrone, thereby avoiding the trade name and at the
same time indicating the quinonoid structure.
The excellent fastness properties of Indanthren blue R encouraged
further research, and many other vat dyes were developed and sold as
108
memebers of the Indanthren range. Other makers have marketed
comparable products under their own brand names; these include the
Algol (Fby), Alizanthrene (ICI) (British Alizarine Co., later ICI), Calcoid
(ACY), and Caledon (ICI, Carbanthrene (NAC), Cibanone (CIBA),
Paradone (LBH), Ponsol (DuP), Sandothrene (S), and Tinon (Gy) ranges
of vat dyes

109
Sulphur Dyes 9
Although dyes of the sulphur class are used in substantial
quantities, there appears to be no justification for providing more than a
brief description here. In spite of their long history little known about the
chemical structure of these dyes. In recent years their importance has
declined, and little needs to be added to the excellent years their
importance has declined, and little needs to be added to be added to the
excellent accounts published during the period 1950 – 1958.
The first commercial sulphur dye was made in France by
Croissant and Bretonniere in 1873. These workers prepared brown dyes
for cotton by heating a variety of organic materials of animal or
vegetable origin with aqueous sodium sulphide or polysulphide. They
also used slightly more complex processes in which the initial products
were baked at temperatures above 200oC; the shade obtained could often
be varied by adjusting the temperature and duration heating. Of the many
dyes examined the only one that attained importance was Cachou de
Laval, obtained by heating sawdust with sodium sulphide. It was
manufactured by several firms for many years, and is still included in the
Color Index (CI Sulphur Brown 1; CI 53000). It may be applied to cotton
from a sodium sulphide bath and fixed on the fibre by aftertreatment with
aqueous potassium dichromate; the resulting shades vary from yellowish
brown to brownish olive.
It was not until 1893 that a sulphur dye was made from
intermediates of known structure. The sulphurisation process was then
applied by Vidal to a great variety of organic substances, and dyes were
obtained that could be fixed on cotton by oxidation. The most important
of these was Vidal Black (CI Sulphur Black 3; CI 53180), obtained from
p-aminophenol or p-phenylenediamine by means of a sullphur melt. In
1897 a better black sulphur dye was manufactured by heating 4-gydroxy-
2’,4. –dinitrodiphenylamine with sodium polysulphide, and this was
marketed by Cassella as Immedial Black V (CI sulphur Black 9; CI
53230). Two years later a further improvement was obtained sulphurisation
110
of the cheap intermediate 2,4-dinitrophenol, and the resulting dye was
produced by AGFA as Sulophur Black T (CI Sulphur Black 1;CI 53185).
Many equivalent products were made by other firms, and the dye is still
of importance. It gives blacks of good fastness to washing and light.
During the years 1897-1902 a great deal of experimental work was
carried out on sulphur dyes, and every available intermediate was
subjected to sulphurisatic. This work led to an extensive patent literature
and the manufacture of many competing ranges of dyes. An almost
complete range of shades was produced, lacking a true red, however.
After 1902 the rate of expansion of this field slackened, but the
occasional introduction of new dyes continued until in 1950s. Table 9.1
gives details of some of the more important sulphur dyes.
Since so little is known of their structures, sulphur dyes are
usually classified according to the chemistry of their starting materials.
The manufacturing processes are chiefly of three types:

1. A dry mixture of the organic starting material (or material)


with sulphur is heated (the temperature usually exceeding
200o C).
2. As 1, but using sodium polysulphide instead, sulphur. The
baking temperature varies widely.
3. The starting material is heated with aqueous sodium
polysulphide, either under reflux or in a closed vessel under
pressure. Some or all of the water may be replaced by
butanol.

The shade and properties of the resulting dyes may vary


considerably with the reaction temperature and duration of heating. In all
cases hydrogen sulphide is evolved during reaction and it is absorbed in
aqueous caustic soda. The dyes are usually isolated from alkaline
solution by air oxidation. Many of them are subject to deterioration
during prolonged storage.
The chemistry of sulphur dyes has been studied by many workers,
and although it has not been possible to assign definite structures the
presence in certain dyes of chromophoric systems of the thiazole (1)
thiazone (2) and thianthrene (3) types has been established. These

111
N S
N

N
S S

1
2
3

and other aromatic nuclei are linked by disulphide or disulphoxide


bridges, which are broken on treatment with sodium sulphide with
formation of –SNa groups, and on reoxidation the disulphide bridges, are
re-formed on the fibre.
The properties of sulphur dyes are intermediate between those of
direct dyes and vat dyes. As already stated, reds are poorly represented,
only dull Bordeaux shades being available. Other hues are plentiful, but
almost all sulphur dyes are somewhat dull. Wet fastness properties are
usually good, but resistance to bleaching is poor. With some notable
exceptions, as in sulphur black T and its equivalents, light-fastness is
only fair or moderate (rarely exceeding SDC grade 5). The great demand
for sulphur dyes is due to their moderately good properties and low cost.
They are applied almost exclusively to cellulosic fibres, the
alkaline batch required being unsuitable for wool and silk. The process
consists in dissolving the dye in a solution of sodium sulphide, whereby
it is reduced to a leuco compound with affinity for the fibre, carrhying
out dyeing just below the boil, then exposing the dyed material to air so
that oxidation and development of the shade take place. Sometimes the
dyeings are aftertreated with a mixture of a dichromate and copper
sulphate for improvement in fastness to light and wet treatments, but this
is liable to result in tendering of the fibre by slow liberating of sulphuric
acid. Cotton dyed with sulphur colours acquires affinity for basic dyes,
and there are sometimes applied as ‘topping’ colours in order to brighten
the shades. Sulphur blacks can also be topped with aniline Black to give
very deep black shades with increased fastness to milling.
A bright green sulphur dye with excellent fastness properties was
formerly included in the ICI range under the name Thionol Ultra Green
B (CI sulphur Green 14). It was a derivative of copper pathalocyanine
containing thiocyano groups which gave a water-soluble mercaptide on
reduction with sodium sulphide. Cotton dyed with this leuco compound
112
is grey, but oxidation in air yields a bright green shade with very good
fastness to light, washing and chlorine. With the advent of green reactive
dyes this product has been superseded.

Sulphurised Vat Dyes:


The sulphurised vat dyes from a small but important group of
products which resemble sulphur dyes in that they are manufactured by
sulphurisation processes but they are applied from a hydrosulphite vat in
the manner of vat dyes. The first of these was introduced by Cassella in
1909 under the name Hydron Blue R (CI Vat Blue 43; CI 53630). It is
obtained by condensing p-nitrosophenol with carbazole in sulphuric acid
medium to form the indophenol and refluxing this (or its leuco

N O

Compound) with dodium polysulphide in butanol. This dye gives reddish


blue shades, and is valuable in that it has better fastness properties than
most blue sulphur dyes and is valuable in that it has better fastness
properties than most blue sulphur dyes and is used as an inexpensive
substitute for indigo. It cannot be completely reduced by sodium
sulphide, and a vat it usually prepared by using a mixture of sodium
sulphide and hydrosulphite.

A greener blue is manufactured similarly by sulphurisation of the


indophenol obtained from N-ethylcarbazole and p-nitrosophenol; this is
Hydron Blue G (Cassella) (CI Vat Blue 42; CI 53640). Several related
dyes have been made by modified processes and by using mixtures of
indophenols.
Attempts have been made to assign a constitution to Hydron Blue
R but its structure has not been firmly established.

113
Ready-reduced and Solubilised Sulphur Dyes:
Many sulphur dyes have been manufactured in a reduced or partly
reduced from and supplied either as solutions or powders, which easily
dissolve in the dyebath with a small amount of sodium sulphide.
Sulphur dyes are also solubilised in the unreduced state by
introducing thisulphonic acid groups, and the resulting derivatives give
clear stable aqueous solutions. They lack substantivity for cellulose until
they have been reduced, but show advantages in freedom from insoluble
matter (especially important in package dyeing), By application of such
products to the fibre from a sodium sulphide bath and exposure to air
dyeings are obtained with the same properties are those of the
corresponding conventional sulphur dyes.

Recent Developments
The Inthion (FH) and Dykolite (Southern Dyestuff Co.) ranges are
sometimes regarded as sulphur dyes, but as their properties differ in
several respects from those of sulphur dyes they are treated separately.

114
Table 9.1 : Examples of Important Commercial Sulphur Dyes
CI Generic CI Consti- Commerci Intermediates Outline of
tution No. al Name Manjufracturing
Process
CI Sulphur CI 53120 Eclipse N,N – Heat with
Yellow 2 Yellow G Diformyl-m- sulphur at 140o
(Gy) tolylene- – 150o C and
diamine rise during 15
+benezidine hr. to 218o –
220o C (ref. 3)
CI Sulphur CI 53160 Immedial 2-(p-Amino- Heat with
Yellow 4 Yellow pheny)-6 sulphur at 190o
GG met6hylbenz – 220o C then
(Cassella) o- thiazole + reflux with aq.
benezidine NaOH and
oxidise with air.
(ref.4)
CI Sulphur CI 53050 Immedial m-Tolylene- Heat with
Orange 1 Orange C diamine sulphur at 215o-
Extra 220o C then
(Cassella) treat with NaOH
(ref. 5)
CI Sulphur CI 53720 Immedial 3-Amino-2- Heat with
Red 6 Red methyl-6- sodium
Brown hydroxy- polysulphide at
3B Extra phonazine 115o – 116o C
(Cassella) (ref. 6)
CI Sulphur CI 53440 Immedial 4-Amino-4 – Heat with aq.
Blue 7 Indone hydroxy-3- Sodium poly-
RR Extra methyldi- sulphide at106o
(Cassella) phenylamine – 112o C, then
oxidise with air
(ref. 7)
CI Sulphur CI 53570 Thional 8- Reflux with aq.
Green 3 Brilliant Phenylamino Sodium poly-
Green 3G - 5-p- sulphide in
(S) hydroxy- presence of
115
phenylamino CuSO4, then
-naphthalene- oxidise with air
1-sulphonic (ref. 8)
acid
CI Sulphur CI 53055 Immedial m-Tolyene- Heat with
Brown 10 Yellow diamine sulphur at 210o
Brown G rising to 250oC.
(Cassella) Dissolve the
product in eq.
Na2S + NaOH,
heat at 240o and
evaporate (ref.
9)
CI Sulphur CI 53185 Immedial 2,4- Heat with eq.
Black 1 Black AT Dinitropheno Sodium poly-
(Cassella) l or 2,4- sulphide under
and many dichloronitro reflux (110o –
other -benzene 120o C), dillute
brands and oxidise with
air (ref. 10)

116
Acid (Anionic) Dyes
10
The most common fiber types to be dyed with acid dyes are
polyamide, wool, silk, modified acrylic, and polypropylene fibres as well
as blends of the aforementioned fibres with other fibres, such as cotton,
rayon, polyester, regular acrylic, etc. Approximately 80-85% of all acid
dyes sold to the U.S. textile industry are used for dyeing nylon, 10-15%
for wool and the balance for those fibres mentioned above. Acid dyes are
organic sulfonic acids; the commercially available forms are usually their
sodium salts, which exhibit good water solubility.
According to their structure, acid dyes belong to the following
chemical groups: azo; anthraquinone; triphenylmethane; pyrazolone;
azine; nitro; and quinoline. Azo dyes represent the largest and most
important group and are followed by antraquinone and traylmethane
dyes. Of the other dye groups, very few products are of any commercial
value.

Acid dyes can be divided into four groups:


(1) These are the level dyeing acid dyes with one sulfinic acid group.
They offer excellent leveling, migration and, coverage of barre
properties. Fastness to light is very good, while the wetfastness
properties in heavier shades generally are only marginal. The latter
can be improved with an aftertreatment of either tannic acid/tartar
emetic or any other synthetic aftertreating agent. The dyes of this
group should be used when wetfastness properties are of no major
concern and when emphasis is put on good dyeing performance,
such as coverage of barre. Typical representatives are CI Acid
Yellow 49, CI Acid Red 337 and CI Acid Blue 40. They can be
used for dyeing of apparel, knit goods, carpet, upholstery, etc.

(2) These are the neutral-dyeing acid dyestuffs. They are also
monosulfonated and are very similar in their leveling, migration,
and coverage of barre properties to group 1; however, because of
117
their chemical structure (larger molecular size), these dyes exhibit
superior wetfastness properties. Since these dyestuffs have
excellent neutral affinity and good build up properties, they are
suited especially for dyeing of medium to heavy shades. CI Acid
Yellow 159 and CI Acid Red 299 are typical dyes of this class.

(3) These are the milling type acid dyes. They are disulfonated dyes
and provide dyeing with highest wetfastness properties. The
leveling and migration properties of these products are much
inferior than those of the monosulfonated dyes in groups 1 and2.
Coverage of barre is also very poor. CI Acid Yellow 79 is an
example of this groups. It is obvious that there are no acid dyes
that combine all desirable properties. Those which offer the
excellent dyeing characteristics such as good leveling, migration
and coverage of barre, have only marginal wetfastness properties;
those that provide high wetfastness do not level very well. The
dyes in group 2 represent the best compromise. When the fabric is
aftertreated with a synthetic aftertreating agent, wetfastness – in
most instances – will be equal or similar to dyeings obtained from
milling dyes.

(4) These are the premetallized dyes which also include mono-and
disulfonated types. Premetallized dyes exhibit are rather high
dyeing strike rate even at pH values of 7-8 and, therefore, are
extremely difficult to dye level. Their wetfastness properties are
either comparable or superior to milling-type acid dyes. CI Acid
Yellow 151 is a representative of this group.

Dyeing Process:
The two major polyamide types commercially available today are
nylon 6 and nylon 66. Nylon 6 represents a polycondensate of
caprolactam, and nylon 66 is a polycondensation product of two
individual components, adipic acid and hexamethylendiamine. Both fibre
types are very receptive to acid dyes under certain conditions.

A direct relationship exits between the chemical structure of an


acid dyes and its dyeing and wetfastness properties. The dyeing of
118
polyamide fibres depends on a great number of variables. Nylon 6 has
greater affinity for dyes than nylon 66 and this may affect fastness
properties of the final dyeing. Heat history of the fibre influences dye
affinity; for instance, heat used during the texturizing process of the fibre
may sometimes vary. Barfre develops as a result. Barre may also be
caused by differences in knitting tension. Antisoil and antistatic fibre has
become increasingly important and it is quite common that these
modified fibres show a reduced dyeability. The dyeing process is
influenced by a number of additional parameters, such as: (a) dyestuff
selection, (b) type and quantity of auxiliaries, (c) ph, (d) temperature, and
(e) time.

(a) Dyes are selected according to the intended use of the fabric to be
dyed. The needed fastness properties and / or dyeing characteristics
determine whether mono or disulfonated acid dyes are used. It is
not advisable to mix these two dyestuff types in a given
formulation, especially not in medium to heavy shades. The
monosulfonated dyes exhaust more rapidly and block the
disulfonated dye from exhausting into the fibre, especially if the
depth of shade is close to the saturation point of the fibre. At
tention also has to be paid to the K value of the individual dyes
within a combination. K values give the dyer an indication of the
sequence in which the dyes of a combination will exhaust onto the
fibre. Since it is most desirable to use on-tone exhausting
combination, the K value of acid dyes in a formulation should not
differ by more than + 0.5-1.0 unit.

(b) When a polyamide is dyed with acid dyes, dyeing assistants are
usually employed. They can fulfill three functions: increase the
leveling and migration properties of acid dyes, help to cover barre,
and improve the compatibility of acid dyes in combinations.

Anionic products show a relatively high affinity for the nylon fibre
at temperatures below the boil and temporarily block dyesites, slowing
down the exhaustion of the dyes and thereby helping to achieve a level
dyeing.

119
Nonionic anionic auxiliaries not only show affinity for the fibre,
but also form complexes with dyes. In this way, they slow down the
exhaustion process and also achieve level dyeing by affecting the
compatibility of the dyes. By proper use of such auxiliaries, normally
incompatible combinations (dyes with substantially different K values)
can become compatible (similar K values, i.e., compatible in presence of
the auxiliary).

(c) The pH is one of the most important factors in dyeing polyamide


with acid dyes. The dyestuff binding groups in a polyamide fibre
are the amino end groups (NH2-). The enable the dissolved and
ionized dye to react with these amino end groups, the latter must
be activated. A very low pH of 3-3.5 provides many activated NH2
groups and results in a rapid, almost instant, exhaust of all the dye
present in the bath. In shuch a case leveling and migration would
be rather poor. At the optimum pH, 85-95% of the dye in the bath
is exhausted onto the fibre at the end of the dyeing cycle. The
most effective pH can be calculated for certain dye combinations.

(d) The dyeing temperature for dyeing polyamide fibres with acid
dyes should be as close to the boil as possible. The higher the final
temperature is, the better are the chances of obtaining a good
dyeing, since the temperature has a great influence on the leveling
and migration properties of acid dyes. Best results in leveling out
fault lots are obtained if the goods are treated at elevated
temperatures of 105-110o C.

Even more critical than the end temperature is the rate of


temperature increase. Depending on the type of dyes used, exhaustion
starts at 25-35o C when using level dyeing acid dyes, or only 50-65o C
when certain milling-types dyes are in the bath. If the correct pH has
been chosen, the dyebath will be exhausted before the boil has been
reached. This also means that it is not always necessary to start a dyeing
at room temperature because there would be, in many instances, a
considerable dead time before the actual exhaustion starts to take place.

120
(e) The dyeing time represents a considerable cost factor in any
process and should be as short as possible without jeopardizing the
quality of the dyeing. Common practice is to sample after 40-45
min at the boil. If dyed under optimum conditions, the dyeing
time at the boil is reduced to 10-20 min.

Dyeing of Nylon Carpet:


A great percentage of acid dyes used in the textile industry is used
in dyeing of nylon and wool carpets. Nylon carpet fibres can be dyed in
many different ways, eg., in raw stock from, where usually highest
wetfastness dyes are applied, in yarn form and in piece form. The latter is
divided into piece or beck dyeing and continuous dyeing. For the
continuous dyeing process, the most popular machine is the Kuesters
carpet-dyeing range, which consists of a wet-out-padder, a dye
applicator, a loop steamer, and 3-4 wash boxes. Usually drying oven is
used after a dyeing range.
Continuous dyeing of nylon carpet became of great interest when
tufted wall-to-wall carpet gained in appeal. The ever-increasing demand
for larger and larger yardages of one particular colour led to the
developments of continuous dyeing ranges which, theoretically, can dye
85 x 103 m2 (1 x 105 yd2) of carpet within 24 hours with no shade
difference from the method used for dyeing solid shades, many
additional dye application techniques have been developed to create the
very popular multicoloured carpet styles. The TAK and Multi-TAK
machines are the most important units which have been added to the
Kuester dyeing range to make it more versatile. Both the TAK and
Multi-TAK represent machines that enable the dyer to apply different
dye liquors in the form of drops or lines or any variation thereof onto the
carpet. Usually, the ground shade is applied first by either padding or
use of the blade; then, before the carpet enters the steamer, additional
colour drops (2-4 different shades) are applied on top of the unifixed
ground shade by either the TAK of Multi – TAK machine. These
droplets form a variety of patterns depending upon the viscosity of the
ground shade colouration, of the TAK droplets and / or of the machine
settings. Some Kuester continuous dyeing machines also are set up in
line with rotary print heads, thereby further widening the styling
possibilities.
121
Dyeing of Wool: Wool has lost its former importance and
represents, today, only a minor factor in fibre dyeing. Dyeing of wool
may be carried out in the various stages of processing. Dyestuff selection
depends upon the specific end uses of the fabric or yarn as well as on the
stage of manufacture. Wool fabrics are dyed primarily by exhaust dyeing
methods. Although continuous dyeing of wool has been discussed for
some time, it has not become very important. Only a few units are
running today which continuously dye wool top and raw stock. Wool is
dyed as: (1) raw stock, (2) yarn and (3) piece goods.

(1) When dyeing raw stock or top the levelness of dyeing is of minor
importance, but the highest possible wetfastness properties for
further processing are required. This does not mean than unlevel
dyeings will be accepted, but that a certain shade variation in the
dyeings can be counter balanced during the blending processes.
According to the requirements for the manufacturing processes,
dye classes with highest wet-fastness premetallized and milling
colours.

(2) For yarn dyeing, the dye selection is governed mainly by the end –
use of the material. However, the subsequent manufacturing
processes influence the selection of dyes as far as fastness
properties are concerned.

(3) For dyeing on piece goods, the performance of the dyes in the
dyebath is very important because a level-dyed piece of fabric is
required above all other aspects. The dye selection for piece
dyeing is, therefore, based on the performance of the dyes as well
as on the fastness requirements for the specific end-uses.

Applicaltion of Acid Dyes to Silk:


Because of economic reasons, very little pure silk is being
processed these days. Blends of silk with other fibres (eg, polyester) are
more common. For fastness reasons, fibre reactive dyes are used quite
frequently, however, when top wetfastness is not needed, selected acid
and neutral premetallized dyes may be utilized. Dyeing is carried out at a
pH 5.0-5.5 with acetic acid and with 0.5% of an ethyxylated fatty acid
122
derivative in the bath. Best exhaustion of acid dyes on silk is achieved at
about 85o C.

Dyeing of Modified Acrylic and Polypropylene:


These fibres in their modified acid dyeable form are of very minor
importance. Regarding acid dyeable acrylic fibres, dyeing procedures are
very specific for the few fibre types available and should be requested
from the fibre producer. With acid-dyeable polypropylene, dyeing is
usually is important to select the proper dyes for modified fibres because
most of them are rather poor in either wetfastness or lightfastness
properties.

123
Basic (Cationic Dyes)
11
The first basic dye, mauve, was synthesized by Perkins in 1856;
and shortly afterward fuchsine, methyl violet, aniline blue, and other
classical basic dyes were developed. For years these dyestuffs were
primarily used for dyeing brilliant shades on silk and cellulosic fibres
that had been treated with a mordant; however, usage of cationic dyes for
these fibres was limited due to very poor washfastness and lightfastness.
Basic dyes did not achieve prominence until the polyacrylonitrile fibres
were introduced in the early 1950s. Initially, acrylic fibres were very
difficult to dye and, until acidic groups were incorporated as dye sites in
the fiber, basic dyestuffs were of little interest. Cationic dyes are
currently used in large quantities to dye acrylics (Orlon, Acrilan, Creslan,
Zefran) and modified acrylics (Verel). Subsequent developments led to
the introduction of acidic groups to polyester and polyamide fibres,
further increasing the market for these dyes.

Dyeing of Acrylic Fibres:


Basic dyes are water-soluble and dissociate into anions and
coloured cations. The cations have a strong affinity for the acidic group
(sulfonic or carboxylic) and form salts. Because of these strong bonds,
washfastness is usually outstanding, and lightfastness varies considerably,
depending on the dyestuff. Basic dyes are usually applied in a batch
process with skein, stock, and package dyeing more prevalent than piece
dyeing on becks or jet machines.
The fundamental steps in the acrylic dying mechanism are:
absorption of the basic dyestuff at the fiber surface, which occurs only
when the glass transition point of the fiber is exceeded; diffusion of the
dye into the fiber as the fiber molecules acquire enough energy to move;
formation of the dye-fiber bond; and migration of dyestuff from the
dyesite to another or from within the fiber to the surface. The degree of
migration varies considerably, depending on the dyestuff, but generally
basic dyes do not migrate well.
124
Leveling of basic dyestuffs can be a major problem which often
can be traced partially to differing exhaustion rates of individual
dyestuffs which may occur in combination shades. One method for
measurement of exhaustion rates is the time of half-dyeing or the time in
minutes required for the fibre to absorb half as much dye as will be
absorbed if dyed to equilibrium. Half-dyeing times do not adequately
describe the behaviour of basic dyestuffs in combinations where the
individual dyestuffs could interfere with each other’s exhaustion rate.
A method has been developed for determining compatibility of K
values. Dyeings of the basic dyestuffs, which are to be rated, are made
in succession for a specified period of time with dyes having a known
strike rate or K value. Five groups (K-1 through K-5) are used to classify
dyes, with K-1 dyes being exhausted first when dyed in combination
with dyes of any other group; dyes with a K-2 are taken up preferentially
when combined with dyes of K-3 to K-5. For optimum leveling, the K
values of basic dyes in a combination shade should be as close to each
other as possible.
Every basic dyeable fiber has a saturation value, i.e, it has given
number of acidic dyesites, which limit the quantity of basic dyestuff that
can be fixed. The dyestuff also has a saturation factor, which is a
measure of the relative molecular weight per caution in the dye. These
two values determine the depth of shade obtainable with a given dye and
fibre.
Acrylic fibres also vary considerably in their rate of dyeing,
depending on whether they are of a dry-spun or a wet-spun fibre. Wet-
spun fibres dye at a higher rate than dry spun fibres.
To overcome the high affinity of some basic dyestuffs and to
prevent unlevel dyeings, often a cautionic retarder is used. Cationic-
dyeable polyester has achieved a moderat3e degree of success because it
lends itself to two-or three colour effects in blends with regular dispense-
dyeable polyester, cellulosic fibres, or wool. Typical basic-dyeable
polyester fibres are Dacron T-64 and T-92, Fortrel 402, and Trevira 640.
The dyeing rate of cationic-dyeable polyester is much lower than
that of acrylic; however, an even greater difference exists in the
diffusibility associated with each, which is estimated for the cationhic-
dyeable polyester to be only 10% of that for acrylics. This has to be
overcome by dyeing at higher temperatures (110-130o C) and by using a
125
carrier to improve penetration. Another use for the carrier is the
prevention of cross-staining the disperse-dyeable protion of the blend by
the basic dyestuffs.
Nonionic products must be present to act as antiprecipitants or to
suspend particles resulting from the reaction between the cationic dyes
and anionic dyestuffs when blends of basic-dyeable and disperse-dyeable
polyester are dyed.

126
Banned Amines
12
Q.1 What are banned amines?

Q.2 What is Eco-Labeling of Textiles?

Q.3 Name the agencies, which have accredited Textiles Committeee


Laboratories?

Q.4 What are the advantages of testing of textiles in an accredited


laboratory?

Q.5 State the list of dyes banned by Government?

Q1. What are banned amines?

Banned amines are the chemicals which are released from some of the
azo dyes on reductive clevage.

Following is the list of amines banned by Germany.


• 4-Amino biphenyl (CAS-No.:92-67-1)
• Benzidine (CAS-No.:92-87-5)
• 4-Chlor-o-toluidine(CAS-No.95-69-2)
• 2-Naphthylamine (CAS-No.:91-59-8)
• p-Chloroaniline(CAS-No.106-47-8)
• 2,4-Diaminoanisole(CAS-No.615-05-4)
• 4,4'-Diamino diphenyl methane (CAS No.:101-77-9)
• 3,3'-Dichloro benzidine (CAS-No.:91-94-1)
• 3,3'-Dimethoxy benzidine(CAS-No.:119-90-4)
• 3,3'-Dimethyl benzidine(CAS-No.:119-93-7)
• 3,3'-Dimethyl-4,4'-diamino diphenyl methane (CAS-No.:838-88-0)
• p-Cresidine (CAS-No.:120-71-8)
127
• 4,4'-Methylene-bis-(2-chloraniline) (CAS No.:101-14-4)
• 4,4'-Oxydianiline (CAS-No.:101-80-4)
• 4,4'-Thiodianiline (CAS-No.:139-65-1)
• o-Toluidine(CAS-No.:95-53-4)
• 2,4-Diamino toluene(CAS-No.:95-80-7)
• 2,4,5-Trimethyl aniline (CAS-No.:137-17-7)
• o-aminoazotoluene (CAS-No.:97-56-3)
• 2-amino-4-nitrotoluene (CAS No.:99-55-8)
• p-amino azo benzene
• 2-methoxy aniline

These are suspected to be carcinogenic and are being banned.

Apart from Germany, Netherlands has also banned the presence of


these amines and this is applicable to clothing, bed linen and footwear.
As per the latest information received, the European Commission has
circulated a working document relating to the restrictions on the
marketing and use of dangerous substances and preparation (azo dyes),
for the consideration of the European parliament and the Council. The
draft proposal aims to restrict the use of 22 amines in textiles and leather
articles.

Q2. What is Eco-Labeling of Textiles?

In order to promote the concept of eco-friendly textiles, a


comprehensive system of eco labels is advocated by European and other
Western countries. For the purpose of issuing eco labels, certain
norms/criteria are stipulated in respect of textile products, on the basis of
Cradle-to-Grave approach. i.e. These criteria are developed on analysing
the product's entire life cycle commencing with extraction of raw
materials, progressing through the stages of production, distribution and
utilisation and disposal after use. The norms are also referred to as Eco
Standards. By and large, these standards are voluntary in nature.
While formulating eco-norms for the issuance of eco labels, at
present the use of 7 different classes of chemicals in textile production
and processing are taken into consideration. These are:
128
• Formaldehyde
• Toxic pesticides
• Pentachlorophenol (PCP)
• Heavy metal traces
• Azo dyes which release carcinogenic amines
• Halogen carriers
• Chlorine Bleaching

The eco standards stipulated by (i) MST, the German Textile


Association, (ii) OTN 100, the famous OEKOTEX Institute from
Austria, (iii) Clean fashion and (iv) Steilmann, the two private eco-label
issuing organisations in Germany are popular in European countries. In
addition to the four-eco labels specified above, a number of private and
national labels are operating in Europe. In some cases these labels are
used solely as a marketing instrument and have little factual and
technical substance. In the face of the proliferation of eco labels, the
Coordination Committee for the Textiles Industries in the EEC
(COMITEXTIL), supports a single European label. Further, it is learnt
that the European Union is finalizing the criteria for a common
"European Community Eco label" (EC-Eco label) after taking into
consideration the criteria specified by other eco labels.

The Government has also evolved eco standards for the eco labeling
of the textile items in consultation with the Indian Textile Trade and
Industry. The criteria for the environmentally friendly textiles including
Cotton, Woolen, Man-made, Jute and Silk products were notified in the
Gazette on October 8, 1996 by Ministry of Environment and Forests. The
eco labeling of textiles notified in the Gazette is a voluntary scheme.
This scheme aims at distinguishing through the agency of Eco-Mark, any
product which is made, used or disposed of in a way that significantly
reduces the adverse effect; it would otherwise have on the environment.
The Earthen Pot is being used as the logo of this scheme.

A comparison of the norms/criteria stipulated for eco parameters in


the popular eco labels operating in Europe and in the Indian Eco Mark
Scheme for textiles are as under:

129
S.# Eco Parameter Criteria/Norms stipulated in ppm
M.S.T OTN Clean Steil- COMIT- Indian
100 Fashion mann EXTIL Eco
Label
Formaldehyde 20 20 50 20 20
(i) Baby Clothing 20 75 75 300 75 75
(ii) Close to skin 75 300 300 500 300 300
(iii) Outer wear 300

Toxic Pesticides 1 5 1 1 0.1 to 1 1


Pentachlorophenol 0.5 -- 0.5 Ban 0.05 to 0.5 0.5
Heavy Metals
(i) Arsenic 0.001 to 0.01
(ii) Lead 0.004 to 0.04
(iii) Cadmium 0.0005 to 0.005 10.0
(iv) Mercury 0.0001 to 0.1 (for all
(v) Copper 0.3 to 100.0 heavy
(vi) Chromium 1 to 20 metals)
(vii) Cobalt 2 to 20
(viii) Zinc 0.5 to 5.0
(ix) Nickel 0.02 to 10.0
Azo dyes Ban BanBan Ban Ban 50.0
containing
carcinogenic
amines
Halogen Carriers Ban --- --- Ban Ban 200.0
Chlorine ___ ___ ___ To avoid Ban ___
Bleaching

Q3. Give the name of agencies, which have accredited Textiles


Committee Laboratories?

Accreditation is a formal recognition that a Testing /Calibration


Laboratory is competent to carry out specific test/s. Such an accreditation
is granted only after the accrediting body (Govt. /non Govt. body or any
third party) is satisfied with a particular laboratory seeking Accreditation.
130
In India, the National Accreditation Board for Testing and Calibration
Laboratories (NABL) is accrediting the laboratories. Apart from this
there are a number of accrediting bodies operating at international level
including A2LA (American Association for Laboratory Accreditation,
USA) and RvA (Raad Voor Accreditate), Dutch Accreditation Council,
Netherlands.
Textiles Committee Laboratories, Mumbai is accredited by Raad
Voor Accreditate, the Dutch Accreditation Council, Netherlands and
National Accreditation Board for Testing and Calibration Laboratories
(NABL) on the basis of its compliance to the relevant criteria which are
based on ISO /IEC Guide 25 and EN-45001. This is the first Textile
Laboratory in India accredited by a reputed Accreditation Board from
abroad.

Q4. What are the advantages of testing of textiles in an accredited


laboratory?

In an accredited laboratory, a documented Quality System is


implemented and its effectiveness is assured. Consequently, the test
reports/certificates issued by the laboratory is readily accepted by the
trade, industry and exporters. The testing services rendered by the
laboratory is qualitatively better than a non-accredited laboratory due to
the following reasons:

The accuracy, repeatability and reproducibility of the test results


are assured;

Qualified and trained manpower is employed for the testing


various parameters;

Standard and validated methods only are used for testing;

The accuracy and precision of the equipments used is ascertained


by periodical calibration using devices traceable to National Standards;
and, the testing of various parameters is carried out under conditions,
which does not affect the accuracy and precision of the test results.

131
Q5. State the list of dyes banned by Government?

The Ministry of Environment and Forests, Government has


prohibited the handling of benzidine based dyes vide the notification
published in the Gazette in January, 1990. As per this notification,
handling of all the 42 benzidine-based dyes is prohibited from 1993
onwards. These are related to banned amines.
The Ministry of Environment and Forests has further prohibited
the handling of 70 more azo dyes, which came under the banned
category as per the notification, published in the Gazette on 26th March,
1997. Thus, the Ministry of Environment and Forests has prohibited the
handling of 42+70=112 dyes which are capable of releasing any of the
harmful amines.

LIST OF 42 BENZIDINE BASED DYES


PROHIBITED FROM 1993

S.No. CI Generic Name CI Constn. No.


1. Acid Orange 45 22195
2. Acid Red 85 22245
3. Acid Black 29 -
4. Acid Black 94 30336
5. Azoic Diazo Compo.112 37225
6. Direct Yellow 1 22250
7. Direct Yellow 24 22010
8. Direct Orange 1 22370
9. Direct Orange 8 22130
10. Direct Red 1 22310
11. Direct Red 10 22145
12. Direct Red 13 22153
13. Direct Red 17 22150
14. Direct Red 28 22120
15. Direct Red 37 22240
16. Direct Red 44 22500
17. Direct Violet 1 22570
18. Direct Violet 12 22550
132
19. Direct Violet 22 22480
20. Direct Blue 2 22590
21. Direct Blue 6 22610
22 Direct Green 1 30280
23. Direct Green 6 30295
24. Direct Green 8 30315
25. Direct Green 8:1 --
26. Direct Brown 1 30045
27. Direct Brown 1:2 30110
28. Direct Brown 2 22311
29. Direct Brown 6 30140
30. Direct Brown 25 36030
31. Direct Brown 27 31725
32. Direct Brown 31 35660
33. Direct Brown 33 35520
34. Direct Brown 51 31710
35. Direct Brown 59 22345
36. Direct Brown 79 30056
37. Direct Brown 95 30145
38. Direct Brown 101 31740
39. Direct Brown 154 30120
40. Direct Black 4 30245
41. Direct Black 29 22580
42. Direct Black 38 30235

LIST OF 70 AZO DYES PROHIBITED FROM JUNE 1997.

S.No. CI Generic Name CI Constn. No.


1 Acid Red 4 14710
2 Acid Red 5 14905
3 Acid Red 24 16140
4 Acid Red 26 16150
5 Acid Red 73 27290

133
6 Acid Red 114 23635
7 Acid Red 115 27200
8 Acid Red 116 26660
9 Acid Red 128 24125
10 Acid Red 148 26665
11 Acid Red 150 27190
12 Acid Red 158 20530
13 Acid Red 167 --
14 Acid Red 264 18133
15 Acid Red 265 18129
16 Acid Red 420 --
17 Acid Voilet 12 18075
18 Acid Brown 415 --
19 Acid Black 131 --
20 Acid Black 132 --
21 Acid Black 209 --
22 Basic Red 111 --
23 Basic Red 42 --
24 Basic Brown 4 21010
25 Developer 14 = Oxidation Base 20 76035
26 Direct Yellow 48 23660
27 Direct Orange 6 23375
28 Direct Orange 7 23380
29 Direct Orange 10 23370
30 Direct Orange 108 29173
31 Direct Red 2 23500
32 Direct Red 7 24100
33 Direct Red 21 23560
34 Direct Red 22 23565
35 Direct Red 24 29185
36 Direct Red 26 29190
37 Direct Red 39 23630
38 Direct Red 46 23050
39 Direct Red 62 29175
40 Direct Red 67 23505
134
41 Direct Red 72 29200
42 Direct Violet 21 23520
43 Direct Blue 1 24410
44 Direct Blue 3 23705
45 Direct Blue 8 24140
46 Direct Blue 9 24155
47 Direct Blue 10 24340
48 Direct Blue 14 23850
49 Direct Blue 15 24400
50 Direct Blue 22 24280
51 Direct Blue 25 23790
52 Direct Blue 35 24145
53 Direct Blue 53 23860
54 Direct Blue 76 24411
55 Direct Blue 151 24175
56 Direct Blue 160 --
57 Direct Blue 173 --
58 Direct Blue 192 --
59 Direct Blue 201 --
60 Direct Blue 215 24115
61 Direct Blue 295 23820
62 Direct Green 85 30387
63 Direct Blue 222 30368
64 Direct Black 91 30400
65 Direct Black 154 --
66 Disperse Yellow 7 26090
67 Disperse Yellow 23 26070
68 Disperse Yellow 56 --
69 Disperse Orange 149 --
70 Disperse Red 151 26130

135
ECOMARK CRITERIA FOR TEXTILES
1. GENERAL REQUIREMENTS:
1.1 The entire textile products manufactured shall meet relevant
standards of Bureau of Indian Standards.
1.2 The product manufacturer must produce the consent clearance
as per the provisions of Water (Prevention and Control of
Pollution) Act 1974 and Air (Prevention and Control of
Pollution) Act 1981, Water (Prevention and Control of
Pollution) Cess Act, 1977 respectively, along with the
authorisation, if required under Environment (Protection) Act,
1986 and the rules made thereunder to BIS while applying for
Ecomark. Additionally, the manufacturer shall produce
documentary evidence on compliance of the provisions related
to noise level and occupational health under the provisions of
Factories Act, 1948 and Rules made thereunder.
1.3 The product packaging may display in brief the criteria based
on which the product has been labelled environment friendly.
1.4 The material used for product packaging shall be reusable or
made from recyclable or biodegradable materials.
1.5 Polyhalogenated based phenolic fire retardants shall not be
used.

PRODUCT SPECIFIC REQUIREMENTS:


A COTTON, WOOL, MAN-MADE FIBRE & BLENDS
S. # Parameters* Max. Limit, mg/kg (ppm)
Baby Close to Outer
Clothing Skin Fabrics
1 2 3 4 5
1. Free & Releasable 20 75 300
Formaldehyde
2. Extractable artificial 0.1 0.1 0.1
sweat/salvia Heavy Metals
Mercury
3. Chromium III 0.1 0.1 0.1
4. Chromium VI Nil Nil Nil
136
Below
detectable
limit
5. Sum Parameters (as lead) 10.0 10.0 10.0
6. Pentachlorophenol (PCP) 0.5 0.5 0.5
(Detectable
limit using
GC.MS)
7. Volatile Hydrocarbons (non- 150 150 150
halogens)
8. Volatile Halogenated 200 200 200
Organics
9. Pesticides (Sum 1.0 1.0 1.0
Parameter)**
10. Banned Pesticides Nil Nil Nil
(Below
detectable
limit)
11. pH of aqueous extract 4.0-7.5 4.0-7.5 4.0-7.5
12. Coupled Amines released 50 50 50
from Azo-dyes (Sum (Detectable
parameters)*** limit using
GC-MS)

* The methods of tests for Eco-parameters are being developed by BIS


and Textiles Committee. Till the methods of test are standardised, the
manufacturer shall declare conformance taking into consideration the
chemicals, auxiliaries and dyes used.

** The list of Pesticides used on cotton, banned restricted or withdrawn


is appended at Appendix A.

*** The list of Coupled Amines released from Azo dyes is appended as
Appendix-B.

137
B. JUTE AND JUTE PRODUCTS
S. # Parameters* Max. Limit, mg/kg
Home Hessians &
Textiles Sockings
&
Clothing
1 2 3 4
1. Free and Releasable
Formaldehyde
Close to skin 75 NA
Outer Fabrics 300 NA
2. Extractable artificial
sweat/salvia
Heavy Metals
Mercury 0.1 NA
Chromium III 0.1 NA
Chromium VI Nil NA
(Below
detectable
limit)
Sum parameters(as lead) 10.0 NA
3. Non-halogenated NA 3%
Hydrocarbon
4. Fatty esters based oil 2% NA
5. Pesticides (Sum 1.0 1.0
Parameter)**
Banned Pesticides Nil Nil
(Below
detectable
limit)
6. PH of aqueous extract 6.0-7.0 6.0-7.0
7. Coupled amines released 50 50
from Azo-dyes (Sum (Detectable
parameters)*** limit using
GC-MS)

138
* The methods of tests for Eco-parameters are being developed by BIS
and Textiles Committee. Till the methods of test are standardised, the
manufacturer shall declare conformance taking into consideration the
chemicals, auxiliaries and dyes used.

** The list of Pesticides used on jute, banned restricted or withdrawn is


appended as Appendix A.

*** The list of Coupled Amines released from Azo-dyes is appended as


Appendix-B.

C. SILK AND SILK PRODUCTS


S. # Parameters* Max. limit, mg/kg (ppm)
Baby Close to Outer
Clothing Skin Fabrics
1 2 3 4 5
1. Free & Releasable 20 75 300
Formaldehyde
2. Extractable artificial 0.1 0.1 0.1
sweat/salvia Heavy Metals
Mercury
Chromium III 0.1 0.1 0.1
Chromium VI Nil Nil Nil
Below
detectable
limit
Sum Parameters (as lead) 10.0 10.0 10.0
3. Pentachlorophenol (PCP) 0.5 0.5 0.5
(Detectable
limit using
GC.MS)
4. Volatile Hydrocarbons 150 150 150
(non-halogens)
5. Pesticides (Sum 1.0 1.0 1.0
Parameter)**
Banned Pesticides Nil Nil Nil
139
(Below
detectable
limit)
6. pH of aqueous extract 4.0-7.5 4.0-7.5 4.0-7.5
7. Coupled Amines released 50 50 50
from Azo-dyes (Sum (Detectable
parameters)*** limit using
GC-MS)

* BIS and Textiles Committee are developing the methods of tests for
Eco-parameters. Till the methods of test are standardised, the
manufacturer shall declare conformance taking into consideration the
chemicals, auxiliaries and dyes used.

** The list of Pesticides used on Silk Worm rearing, banned restricted or


withdrawn is appended as Appendix A.

*** The list of Coupled Amines released from Azo dyes is appended as
Appendix-B.

APPENDIX-A

1. PESTICIDES REGISTERED FOR USE ON COTTON

Herbicides:
Alachlor, Diuron, Fluchlosalin, Monosodium methanearsonate
(MSMA), Paraquat Dichloride, Trifluralin.

Fungicides:
Carbendazim, Cuprous oxide, Streptomycin & Oxytetracycline,
Thiram.

Insecticides:
Acephate, BHC, Carbaryl, Carbofuran, Chlorpyriphos, Cypermethrin,
Decamethrin, Dicofol, Diflubenzuron, Dimenthoate, Endosulfan,
Fenitrothion, Fenthion, Fenvalerate, Fluvalinate, Lindane,
140
Malathion, Methyl parathion, Monocrotophos, Nicotine sulphate,
Oxydemeton methyl, Permethrin, Phenthoate, Phorate, Phosalone,
Phosphamidon, Pyrethrum, Quinalphos, Alphamethrin, Methomyl,
Triazophos, Cartap hydrochloride, Neem based products,
Carbosulfan (for cotton seed), Fenpropathrin, Bacillus
thuringensis.

Plant Growth Regulators:


Chlorocholine Chloride (CCC) or Chlormequat Chloride.

2. PESTICIDES REGISTERED FOR USE ON JUTE IN INDIA

HERBICIDES: Dalapon

FUNGICIDES: Carbendazim

INSECTICIDES: Carbaryl, Carbofuran, Endosulfan, Lindane, and


Phosalone.

3. PESTICIDES USED DURING REARING OF SILK WORM

INSECTICIDES: Dichlorvos

FUNGICIDES: Carbendazim

DITHIANON:
Extract from list of pesticides not approved, restricted use,
withdrawn or banned in the country as on 10.04.1992.

(i) Pesticides not approved for use:


2, 4, 5-T

(ii) Pesticides restricted for use:


Use of DDT in agriculture is banned. In very special
circumstances warranting the use of DDT for plant protection, the State
or Central Government may purchase it directly from M/s. Hindustan
141
Insecticides Ltd. to be used under expert Government supervision. Use of
DDT for public health programme upto 10,000 MT per annum, except in
case of any major outbreak, is restricted.
Use of Lieldrin shall be restricted for Locust Control in desert
areas by Plant Protection Adviser to the Govt. of India.

(iii) Pesticides banned/withdrawn:


Pentachlorophenol, Toxaphene and Aldrin

APPENDIX-B
Coupled Amines released from Azo dyes

1. 4-Aminodiphenyl
2. 2-Amino-1-nitrotoluene
3. Benzidine
4. 4-Chloro-o-toluidine
5. 2-Naphthylamine
6. O-Aminoazotoluene
7. p-Chloraniline
8. 2, 4’-Diaminoanisole
9. 4, 4’-Diaminodiphenylmethane
10. 3, 3’-Dichlorobenzidine
11. 3, 3’-Dimethoxy-benzidine
12. 3, 3’-Dimethylbenzidine
13. 3, 3’-Dimethyl-4, 4’-diaminodiphenylmethane
14. P-kresidin (2-Methoxy 5-methylaniline)
15. 4, 4’-Methylene-bis-(2-chloraniline)
16. 4, 4’-Oxydianiline
17. 4, 4’-Thiodianiline
18. 0-Toluidine
19. 2, 4-Toluyendiamine
20. 2, 4, 5-Trimethylaniline
21. p-Amino-azobenzene
22. 2-Methoxyaniline
142
Fastnes Properties of Dyes
13
In an age of consumer activism and increasing international trade,
test methods and procedures assume more and more importance.
Generally accepted tests, instruments, and standards provide a
common basis for the evaluation of quality aspects of dyed textiles.
In the development of text methods, an attempt is made to make
them broad in scope and related to actual process in use. Such tests are
generally of an accelerated nature, i.e., they reveal the fastness properties
exhibited by the material over a lengthy period of time in a test of short
duration.
Fastness of dyed textiles is evaluated in regard to natural
destructive agents, such as daylight, weather, and atmospheric gases, as
well as to various treatments the material is likely to undergo, such as
washing, drycleaning, ironing, steaming, etc.
The international body active in test method development is the
ISO (International Standards Organization). Fastness tests for dyed
textiles fall under the jurisdiction of ISO Technical Committee 38
Textiles / Subcommittee 1 “Tests for Coloured Textiles and Colorants.”
The United States is represented in ISO through the American National
Standards Institute (ANSI). In the field of interest here, ANSI relies on
the American Association of Textile Chemists and Colourists (AATCC)
for test development and expert guidance. The AATCC currently has 15
active research committees concerned with colourfastness properties.
The purpose of these Organizations in this area is solely to provide
useful test methods. The setting of specifications on the basis of such test
methods is a matter to be resolved between buyer and seller.

COLOURFASTNESS:
Described below are the essential features of generally accepted
tests (from the AATCC 1976 Technical Manual) used in evaluating
fastness proper;ties of dyed, printed or otherwise colored textiles. For
143
complete details and for sources of the specialized materials and
equipment used in some of these test procedures, reference should be
made to the current AATCC Technical Manual.

Acids and Alkalies:


This test method is designed to reveal the colourfastness of dyed
or printed textiles to acid fumes, sizes, alkaline sizes, alkaline cleaning
agents, and alkaline street dirt, by steeping the textile material in or
spotting with the required solutions. The tested specimens are examined
for changes in colour.

Procedure:
Acid tests: (1) The coloured material is spotted with hydrochloric
acid solution (100 ml 35 wt % HCI soin) at 21o C and allowed to
dry at room temperature without rinsing; and (2) The coloured
material is spotted 56% acetic acid and allowed to dry at room
temperature without rinsing.

Alkaline tests: (1) The coloured material is steeped for two


minutes at 21o C in ammonium hydroxide solution (28 wt% NH3)
and dried at room temperature without rinsing; (2) The coloured
material is steeped for two minutes at 21o C in a 10% sodium
carbonate solution and dried at room temperature without rinsing,
(3) The coloured material is hung in a 4-L bell jar placed on a
glass plate over a 7.6-cm evaporating dish containing 10 ml of
concentrated ammonium hydroxide (28 w% NH3). A 24-h
exposure is made; and (4) The coloured material is spotted with a
freshly prepared calcium hydroxide paste, allowed to dry, and then
brushed to remove the dry power.

EVALUATION AND CLASSIFICATION:


The effect on the colour of the test specimens is expressed and
defined by reference to the Gray Scale for Evaluating Change in Colour.
The results are reported as to class with respect to the specified test.

144
Colourfastness to Bleaching with Chlorine (AATCC 3-1975) ANSI L
14.57-1973/R 1963):
This test method is used to determine the effect of sodium
hypochlorite containing up to 0.3% available chlorine on dyed or printed
cotton or linen textiles.
Procedure:
The specimens are washed in sodium hypochlorite solutions under
controlled conditions at pH 11-0 = 0.2 and temperatures of 27+-3o C for
60 min.

Test I I III IV
Available chlorine, 0.01 0.1 0.2 0.3
%

Controls:
The correct test performance is checked with the aid of two
control dyeings: Control 1 is a dyeing on cotton cloth of 4% of Vat
Violet VN [4424-87-7] (CI Vat Violet 13), 10% paste`; and Control 2 is
a dyeing on cotton of 40% Vat Brilliant Violet RK [3076-87-7] (CI Vat
Violet 17), 10% paste.

EVALUATION AND CLASSIFICATION:


Five classes of fastness are established with the help of the Gray
Scale for Evaluating Change in Colour. Control 2 fabric, when exposed
to the four tests under satisfactory conditions well shows the following
classifications:

Test I I III IV
Classification 4 4-3 3 3-2

Colourfastness to Bleaching with Peroxide (AATCC 101-1975)


(ANSI L 14.146-1973):
This test is applicable to textiles of all kinds in all forms, with the
exception of polyamides.

145
Procedure
A test specimen is placed between two 10.2 x 3.8 cm white test
cloths, one of which is made of the same fabric as the specimen
and the other of which varies as follows: If the first piece is wool,
silk, linen, or rayon, the second piece should be cotton or
multifiber fabric, if the first piece is cotton, or acetate, the second
piece should be viscose rayon or multifiber fabric.

The coloured swatch is placed between the two white cloths and
sewn on all four sides, then subjected to the required test is rolled
loosely and place in a test tube with the appropriate solution for
the indicated time. In test IV, the swatch is placed in saturated
steam (99-101o C) for 1 hour.

TABLE: 3
CONDITIONS IN TESTING FOR COLOURFASTNESS TO
BLEACHING AND PEROXIDE
Test Conditions Wool, I Silk, II Cotton, III Cotton, IV
35% hydrogen 15.4 8.8 8.8 8.8
peroxide, (17.5g) (10.Og) (10.Og) (10.Og)
a
mL / L H2O
Sodium silicate; 1.41 5.1 4.2 7.0
sp gr (7.2g) (6.Og) (10.Og)
o a
(42 Be) mL / L H2O
Sodium 0.5
pyrophosphate,
g / L H2Oa

Sodium hydroxide, g 0.5 0.5


/ L H2Oa,b

Wetting agent, mL/L 2.0


H2Oa

pH, initial 9.0-9.5 10.5 10.5 10.5

146
Table 3 Cont.

Test Conditions Wool, I Silk, Cotton, Cotton,


II III IV
Time, h 2 1 2 1
liquor / cloth 20:1 30:1 30:1 1:1
ration
• Distrilled water.
• Doubly sulfonate coaster oil.

EVALUATION AND CLASSIFICATION:


Staining and / or mark-off evaluated using either the AATCC
Chromatic Transference Scale, or the Gray Scale for Evaluating
Staining. Change of shade is evaluated by means of the Gray Scale for
Evaluating Change in Colour.

Carbonizing (AATCC 11-1975) (AMSI L 14.3-1973/R 1960):


Carbonizing is the process to which wool is subjected in order to
remove impurities (such as burrs, bark, grass and cotton fibres) by
soaking in a strongly acid solution. The stock or fabric is then dried and
baked, after which the cellulosic material may be beaten or washed out.
This test method reproduces any colour change encountered in the
carbonizing operation, and inapplicable to dyed wool textiles.

Procedure:
Four specimens of worsted test cloth (containing 12-effect floats
of accetate, Acrilan 36, Arnel, cotton, Creslan 61, Dacron 54,
Dacron 64, nylon 66, Orlon 75, silk, Verel A and viscose) are
dyed. One is kept for comparison, and each of the other three is
stirred and squeezed for 10 min at 24oC in 100 ml of sulfuric acid
solution (50% g/L, or 6o Twad). The specimens are wrung to
allow 60-80% pickup, dried at 80% pickup, dried at 80o C for 15
min, and then baked for 15 min at 110o C.

At this point, one sample is saved to show any change in shade


while still strongly acid. A second sample is rinsed in running
water for 30 min, and the third sample is rinsed twice in distilled
147
water, then in a dilute soda ash solution, and finally in running
water (rinsing is continued until the sample is neutral or slightly
alkaline to litmus paper).

EVALUATION AND CLASSIFICATION:


The test specimens are examined by comparison with dyed
standards and classified as follows: Class 1. Poor fastness – a colour
which changes seriously in the acid bath and does not return to shade on
rinsing; Class 3. Good fastness-a colour which changes materially in the
acid bath but returns to shade on rinsing, and Class 5. Excellent fastness
– a colour which is unaffected by the entire process of carbonization.
Evaluation may also be based on the Gray Scale for Evaluating
Change in Colour.

Standards:
Standards for Classes 1,3, and 5 are dyed with the following dyes:
Class 1.2% Alizarine Red S (topchrome) [130-22-3] (CI 58005); class
3.2% Acid Cyanine (dyed acid) [6488-97-1] (CI 50230); and Class 5.2%
Alizarine Irisol R (dyed acid) [4430-18-6] (CI 60730).

Crocking (AATCC 8-1974/116-1974) (ANSIL 14.74-1973/ASSIL


14.212-1973):
This test determines the fastness of a dyestuff to either wet or dry
rubbing.

Procedure:
The test specimen is placed on the base of the Crockmeter and a
square of white test cloth is rubbed on the coloured specimen by
means of the Crockmeter finger (dry test cloth for dry crocking;
test cloth wet out in distilled water for wet test; wet pickup 65+-
5%). The sample is rubbed twenty times; after this the staining of
the white cloth is determined.

CLASSIFICATION AND EVALUATION:


Staining is graded by use of the AATCC Chromatic Transference
Scale or the Gray Scale for Evaluating Staining.

148
Degumming (AATCC 7-1975) (ANSI L 14.4-1973):
This test is applicable to dyed silk yarn which may be subjected to
a degumming operation (boil-off in soap solution) during manufacture.
Procedure:
The dyed yarn in braided with undyed gum-silk yarn and boiled
for 2 h in 0.5% soap solution at a constant 100: 1 liquor ratio, then
rinsed cold, and air dried.

EVALUATION AND CLASSIFICATION:


Alterations in colour or staining of undryed silk are observed and
rated by comparison with dyed standards or by use of the Gray Scale for
Evaluating Staining or the AATCC Chromatic Transfer Scale.

Standards:
The standards are dyed as follows: Class 3.5% Indigo MLB/6B
Power [6417-56-7] (CI 73075). Class 5.5% Indigo MLK / 4B Powder
[2475-31-2] (CI 73065).

Drycleaning (AATCC 132-1976) (ANSI L 14.241-1970):


This test indicates the effect of repeated commercial drycleanings,
using prechloroethylene as solvent, on dyed and printed fabrics. It is
applicable for evaluating the colourfastness of all fibres, fabrics, and
yarns which are intended for apparel or household use, and which are
likely to be commercially drycleaned. The test is not intended to evaluate
the resistance of colours to spot or stain – removal procedures.

Procedures:
Samples (10 cm X 4 cm) are placed in a 10 cm X 10 cm bag of
undyed cotton twill fabric together with 12 stainless steel disks
30+ 2 mm diameter and 3 + 0.5 mm thickness. Samples are run
with 200 ml. Percloroethylene for 30 min at 30 + 20o C, after
which they are blotted and air-dried.

EVALUATION AND CLASSIFICATION:


Sample are evaluated for colour change by comparison with the
Gray Scale for Evaluating Change in Colour.

149
Fulling (AATCC 2-1975):
Fulling is a finishing process for woolen cloth involving the effect
of heat, moisture, soap, and mechanical pounding. The purpose of this
process is to shrink the cloth by felting action and thus make it firmer
and thicker. The fulling test is devised for evaluating the colourfastness
of dyed wool fabrics or yarns to mill fulling.

Procedure:
Two gram dyed wool and two-gram white test cloth are formed
into a bag, dyed sample inside. Then 6.3 mm steel balls are placed
inside the bag. Tests are carried out under controlled conditions as
shown in Table 4, in the Launder-Ometer using 20-cm steel tubes
and 8 ml of solution. Yarns may be braided with white wool or
other yarn.

TABLE: 4
TEST CONDITION IN THE FULLING TEST

Test Temp. o Soap conc, Na2CO3 Time, h


C wt% conc, wt%
I 32 3.75 1.5 0.5
II 38 3.75 1.5 1.5
III 43 3.75 1.5 4.5

EVALUATING & CLASSIFICATION:


The specimens are evaluated by running comparative tests against
standard dyeings which represent minimum fastness for each class with
respect to alteration of colour staining. As an alternative, the Gray Scale
for Evaluating Staining or the AATCC Chromatic Transference Scale
may be used.

Standards:
Class1. 1% Alizarine Sky Blue B [6424-75-5] (CI 62105). Class
3.2% Brilliant Milling Blue B [5863-46-7] (CI 42645), and Class 5.2%
Eriochrome Azurole B [1796-92-5] (CI 43830).

150
Dry Heat (Excluding hot Pressing) (AATCC 117-1976) (Based On
ISO R 105/IV Part 2):
This method assesses the resistance of the colour of textiles of all
kinds and forms to the action of dry heat, but excludes hot pressing.
Procedure:
The material under test is standwiched between a piece of undyed
material of the same type as the test sample and a piece of
multifiber test fabric No.10A. The composite test sample is
exposed for 30s to one of the temperature conditions listed in
Table 5 in a heating device such as the Scorch Tester.

EVALUATION AND CLASSIFICATION:


The change in colour of the test specimen is rated with the help of
the Gray Scale for Evaluating Colour Change. The staining of the undyed
fabric (s) is evaluated using the Gray Scale for Staining or the AATCC
Chromatic Transference Scale.

Hot Pressing (AATCC 133-1976):


Coloured samples are tested for dry, damp and wet pressing under
controlled conditions.

Procedure:
A 12 cm x 4 cm piece of material is exposed in a Scorch Tester.
The bottom plate of the heating device is covered with asbestos
sheeting, wool flannel, and dry, undyed cotton fabric. In case of
dry pressing, the dry sample is placed on top of the cotton fabric.
The top plate of the deveice is lowered for 15 at either 110 + 2o C,
150 + 2o C. In damp pressing, the sample is covered with a piece
of undyed cotton fabric that has been soaked in distilled water and
squeezed to contain its own weight of water. In wet pressing, both
the test sample and a piece of undyed cotton are soaked in distilled
water and squeezed to contain their own weight in water. The wet
test sample is placed on top of the dry cotton cloth and covered
with the wet cotton cloth.

151
TABLE: 5
TEMPERATURE CONDITIONS FOR COMPOSITE TEST
SAMPLE
Test Temperature, o C
AATCC
I 149 + 2
II 163 + 2
III 177 + 2
IV 191 + 2
V 205 + 2
VI 219 + 2
ISO
I 150 + 2
II 180 + 2
III 210 + 2

EVALUATION AND CLASSIFICATION:


For determining change in colour, samples are evaluated immediately
and after the sample have been allowed to condition for 4 hours at 20o C,
using the gray Scale for Evaluating Colour Change, and staining is
graded by comparison with the AATCC Chromatic Transference Scale
the Gray Scale for Evaluating Staining.

Lightfastness:
The 1976 edition of The AATCC Technical Manual lists six tests
for lightfastness: sunlight, daylight; carbon arc, alternate light and
darkness; water-cooled xenon arc, continuous; and alternate light and
darkness for both carbon arc and xenon arc.

Lightfastness (General Method) (AATCC 16-1974):


Samples and standards are properly mounted, partially covered,
and exposed for the appropriate number of hours under specified
conditions.

152
CLASSIFICATION AND EVALUATION:
Samples can be evaluated by three methods:

1. Based on AATCC blue-wool standards L2 through L9, as shown


in Table 6. Lightfastness is evaluated in terms of colour-change
comparison with standard.

2. Based on standard sample. When an agreed-upon standard on


sample are exposed until the standard shown a change equal to
step 4 on the Gray Scale for Evaluating Colour Change, the
sample is considered satisfactory if no greater break appears, and
unsatisfactory if a greater break is apparent.

3. AATCC Standard Fading Units. Samples may be classified


according to the number of Standard Fading Units necessary to
products a change equal to step 4 on the Gray Scale for Evaluating
Change in Colour.
TALE: 6

CLASSIFICATION BY LIGHTFASTNESS

Colour change
Less Equal More than Class
than
L2 1
L2 L3 2
12 L3 2-3
L3 L4 3
L3 L4 3-4
L4 L5 4
L4 L5 4-5
L5 L6 5
L5 L6 5-6
L6 L7 6
L6 L7 6-7
L7 L8 7
L7 L8 7-8
153
L8 L9 8
L8 L9 8-9
L9 9

Either the single step or the two step method can be used. In the
single step method, the sample is faded to a step 4 break of the Gray
Scale. In the two-step-method, a preliminary judgement is made when a
step 4 break is obtained, then the sample is exposed further until step 3
break is obtained. If the two result differ, both are reported.

Lightfastness-Carbon Arc (AATCC –16-A-1974):


Partially covered sample and standards are exposed and examined
after periods as are necessary to produce a “just appreciable fading”
Classification may be by any method given under General Method in this
procedure.

Sunlight-Fastness (AATCC 16B-1974):


Partially covered samples and standards are exposed in a glass
covered exposure cabinet and are allowed to remain in the cabinet only
on sunny days during the hours between 9 am 3 am (Standard time); they
are removed for inspection at frequent intervals. As such standard,
beginning with L2, shows a change equal to step 4 on the Gray Scale for
Evaluating Change in Colour, all samples that show an equal change are
removed from the cabinet.
Samples are classified as in the carbon arc method, using AATCC
standards or a standard sample. When desired, a standard agreed upon
by the buyer and seller may be used in place of the AATCC standards.
In this case, exposure is continued until the sample agreed upon shows a
change equal to step 4 on the Gray Scale for Evaluating Change in
Colour.
Exposure time may be based on a mutually agreed upon number
of langleys (4.184 x 104 J/m2) of radiation. When a stated number of
langleys are used, classification is based on the Gray Scale for
Evaluating Change in Colour. A sample that shows no greater change
than step 4 is considered satisfactory. Classification may also be used on
the required number of langleys (4.184 x 104 J/cm2) necessary to cause a
154
change equal to step 4 on the International Geometric Gray Scale. The
report should include the method used as well as the date and location of
testing.

Daylight Fastness (AATCC 16C-1974):


Tests are conducted as for sunlight-fastness except that exposed
samples are allowed to remain in the exposure cabinet 24 hours a day,
and are removed only for inspection. Classification is as for sunlight
testing.

Lightfastness Carbon Arc Alternate Light Darkness (16D-1974):


This method requires a carbon arc machine that is equipped with
an atomizer, and which automatically controls the turning on and off the
lamp. A cam producing 1 h of darkness and 3.8 h of light is used. The
apparatus is adjusted so that during the light-on period the black panel
temperature is 63 + 3o C, and the rh 35 + 5%. During the 1-h period the
relatively humidity is 90 + 5%. Classification and evaluation are based
on AATCC blue wool standards or on a standard sample.

Lightfastness-Xenon Lamp-Continuous Light (AATCC 16E-1976):


Sample are exposed in the same manner as in the carbon arc machine
with the black-panel temperature at 63 + 3o C and rh of 30 + 5%.
Evaluation and classification are based on AATCC blue-wool standards
or on a standard sample.

Lightfastness-Xenon Lamp-Alternate Light-Darkness (AATCC 16F-


1974):
This method uses a cam as in Method 16D-1974 and follows the
same procedure with the xenon tube replacing the carbon arc as a light
source.

Carbon-Arc Lamp (Fade-Ometer):


The Fade-Ometer is operated on arc at 15-17 A and 125-145 V
across the arc. The are is enclosed in a heat-resistant glass globe. The
samples are mounted 25 cm from the arc and are on a frame that revolves
about the arc 2 + 1 times per minute. A blower unit in the base provides
as flow of air through the machine allowing for temperature control,
155
which is measured by use of black-panel thermometer. The humidity in
the chamber is automatically controlled.

EXPOSURE CABINET:
The exposure cabinet for sunlight or daylight tests is constructed
so as to face due sought in the Northern Hemisphere, and due north in
the Southern Hemisphere, with a slant approximately equal to the degree
of latitude at which the cabinet is located. It allows free access of air to
the samples and is covered with window glass at least 8 cm above the
exposure area.

Black-Panel Thermometer:
The unit consists of bimetallic diatype thermometer mounted on a
suitable frame with the face (plate) of the frame and stem of the
thermometer sprayed with a head resistant black enamel.

Lightfastness Standards:
Eight lightfastness L2 through L9 are available from AATCC.
These standards are prepared by blending very proportions of wool dyed
with a very fugitive colour, Eriochrome Azural B (1796-92-5] (CI
43830), and wool dyed with a fast colour. Indigosol Blue AGG [4086-
05-9] [CI 173801], in such a manner that each numbered standard is
approximately twice as fast the preceding numbered standard.

Xenon-Arc Lamp:
The apparatus uses a 1quartz-xenon burner tube which is water-
cooled, with an inner Pyrex (Corning Glass Works) filter glass and an
outer filter of clear glass. Samples are mounted at the required distance
from the arc and are supported on a frame which revolves about the arc 2
+ 1 times per minute. Testing temperatures are measured by the black-
panel thermometer, and moisture is added by controlled methods.

Alternate Wash-and-Light (AATCC 83-1974):


This test is designed to provide a consumer end-use test which
will simulate an average of five exposure to sunlight (duration, 6 h)
followed by a washing without chlorine.

156
Procedure:
A 6 cm X 15 cm specimen is exposed for twenty Standard Fading
Units and is followed by a Wash IIIA.

EVALUATION:
The effect on the colour is greater and expressed by comparison
with the Gray Scale for Evaluating Change in Colour.

Phototropism (AATCC 139-1975):


This test is designed to show colours that are changed
impermanently when exposed to strong light. This change takes place
after a short exposure, but the colour returns to its original shade when
placed in the dark.
Procedure:
Dyed samples 6 cm X 3 cm are exposed in the xenon arc fading
apparatus for 1/25 of the time necessary to obtain a step 4 Gray
Scale Fade on an L-2 blue-wool standard. The sample is
immediately inspected for a contrast between the original and the
exposed portions. If the contrast is equal to or less than a step 4 of
the Gray Scale for Evaluating Change in Colour, the sample is
considered not phototropic. If the contrast is greater than step 4,
the specimen is left in the dark for one hour at 20 + 2o C and a rah
65 + 2o C. If the contrast has not disappeared, the sample is
exposed for 15 to steam at 101 kPa (1atm) and reinspected. If the
disappears, the sample is considered to be phototropic. If the
contrast remains, the sample is not considered phototropic and the
contrast is due to low lightfastness. Fastness to light should be
assessed in a parallel test.

OZONE IN THE ATMOSPHERE UNDER LOW HUMIDITY


(AATCC 109-1975) (ANSI L 14174-1973):
It has been found that ozone can destroy dyes applied to textiles.
This test has been devised to expose and determine the fastness of dyed
textiles to ozone at rh not exceeding 65%.

157
Procedure:
A specimen 10 cm x 6 cm and a swatch of Control No.109, are
suspended in a exposure chamber at 18-28o C with rh <65%.
Ozone should be present in concentrations that produce one cycle
of fading 1.5-6 h of test. Samples are exposed for the number of
cycles necessary to cause a change of shade. A cycle is considered
complete when the control matches the Standard for Fading.
Usually two cycles will cause a change in an ozone-sensitive dye.

EVALUATION AND CLASSIFICATION:


Sample are granted by comparison with the Gray Scale for
Evaluating Change in Colour and the report will include the number of
cycles to which the sample has been subjected.

Ozone in the Atmosphere Under High Humidity (AATCC 129-


1975):
This test is analogus to the pregious test except that the test
specimen is exposed in a chamber at 40 + 5o C and 85 + 5% rh, together
with control sample No.129.

Bumed Gas fumes (AATCC 23-1975) (ANSIL 14.56-1973):


This method accesses the resistance of coloured textiles when
exposed to atmospheric oxides of nitrogen as derived from the
combustion of heating gas.

Procedure:
Test specimens (5 cm X 10 cm) are exposed together with a strip
of Control Sample, No.1, in a gas-fading apparatus, until the
control sample shows a change in colour corresponding to that of
the standard of fading. The gas-fading apparatus contains an open
flame from combustion of illuminating gas or butane.

EVALUATION:
After each exposure cycle the specimens are compared with
unexposed samples. The effect, if any, is classified with the aid of the
Gray Scale for Evaluating Change in Colour. The class number and the
number of exposure cycles are reporte.
158
Washfastness:
Washing, Domestic and Laundering, Commercial: Accelerated
(AATCC 61-1975) (ANSI L 14.81-1973): These accelerated laundering
tests are designed for evaluating the washfastness of textiles. One 45 min
test approximates the colour loss and/or abrasive action of five average
hand, commercial, or home launderings.
The conditions of the four different tests are given in Table-7.

Procedure:
Samples (5 cm X 10 cm (Test IA) or 5 cm X 15 cm (all other
tests)) to which a 5 cm X 5 cm piece of multifiber fabric has been
seen or stapled along one side are filled one each into 7.5 cm X
12.5 cm or 9 cm X 20 cm stainless-steel cylinders. The wash
liquor and the steel balls as per Table 7 are added. The detergent
used is AATCC Standard Detergent WOB. The containers are
closed and subjected for 45 min at the required temperature in a
Launder Ometer (Atlas Electric Devices Inc.). At the end of the
cycle, the containers are removed and the samples rinsed twice in
100 ml of water for 1 min at 40o C. They are scoured in 100 ml of
0.014% soln of acetic acid for 1 min at 27o C and rinsed again for
1 min at 27o C in water. The sample are then hydroextractred and
dried by pressing with an iron at 135-150o C.

TABLE: 7
TEST CONDITIONS

Test Temp, Total liquor Detergent Available Number Time,


o
No. C volume mL of Total Chlorine of steel min
volume,% of total balls
volume %
IA 40 200 0.5 10 45
IIA 49 150 0.2 50 45
IIIA 71 50 0.2 100 45
IVA 71 50 0.2 0.015 100 45

159
EVALUATION:
Test IA conforms to five careful hand launderings at 40o C. Test
IIA conforms to five commercial launderings at 38o C or five home-
machine launderings at medium or warm temperature setting. Test IIA
conforms to five commercial launderings at 49o C or five home launderings
at 60o C. Test IVA conforms to five commercial launderings at 71o C or
five home launderings at 60-66o with chlorine present. Samples are
evaluated for change in colour with the corresponding Gray Scale and for
staining with the aid of the AATCC Chromatic Transference Scale or the
Gray Scale for Evaluating Staining.
MISCELLANEOUS FASTNESS PROPERTIES

Prespiration (AATCC 15-1976):


Prespiration may cause an undesirable change in shade or staining
or both. This test is applicable to dyed, printed or otherwise coloured
fabrics.

Procedure:
A 5.7 cm x 5.7 cm swatch backed with No.10 multifiber test cloth
is immersed in the test solution for15-30 min and squeezed to 2-2
½ times its original weight. The samples are placed between glass
or plastic plates and stacked in the AATCC. Prespiration Tester or
in Prespirometer. A 3.63 kg weight is added to the Prespiration
Tester or 69-kPa (10 psi) pressure is adjusted on the Prespirometer.
The loaded specimen unit is heated in an oven at 38 + 1o C > 6 h.

The acid solution (pH 3.5) is made up of 10.00g sodium chloride;


1.00 g of 85% lactic acid (USP); 1.00 g disodium hydrogen phosphate
anhydrous, Na2HPO4; and 0.25 g histidine monohydrochloride; the
solution is brought to one litre with distilled water.

EVALUATION AND CLASSIFICATION:


Samples are evaluated for colour change by comparison with the
Gray Scale for Evaluating Change in Colour. Four evaluation of staining,
either the AATCC Chromatic Transference Scale or the Gray Scale for
Staining may be used.

160
Steam Pleating (AATCC 131-1974):
This test is applicable to textile intended to be used in pleated
clothing. It is designed to measure the change in shade of dyed textiles
that are subjected to a steam treatment, as in pleating.

Procedure:
A 4 cm X 5 cm specimen is placed between two 4 cm X 5 cm
pieces of undyed scoured fabric of the same type of fiber used in
the test specimen and sewn along one side. The specimen is then
mounted on a special Specimen Holder and steamed under one of
the following three conditions:

Test Time, Temperature, Pressure,


min oC kPa
I mild 5 108 34
II 10 115 69
intermediate
III sever 20 130 173

After exposure the samples are air dried below 60oC and
conditioned for 4 h at 20 + 2o C and 65 + 2% rh.

EVALUATION:
The change in colour of test specimen is evaluated with the Gray
Scale for Evaluating Colour Change. The staining of the undyed fabric
pieces is evaluated with the Gray Scale for Evaluating Staining. The type
of test and the ratings figures are reported:

Stoving (AATCC 9-1975) (ANSI L 14.9-1973):


Stoving is a method for bleaching wool by subjecting it to sulfur
dioxide fumes. This test is applicable to dyed yarns of all kinds, which
might be subjected to the sulfur dioxide stoving procedure.

Procedure:
The dyed yarn is braided with undyed wool and undyed silk,
soaked in 0.5% soap, hung in a bell jar with an excess amount of

161
burning sulfur dioxide fumes for 16.h. After through rinsing in
cold water and extraction, the sample is dried and evaluated.

EVALUATION AND CLASSIFICATION:


Samples are evaluated in comparison with dyed standards, or by
comparison with the Gray Scale for evaluating Change of Colour.
Staining of the undyed materials is evaluated with the AATCC
Chromatic Transference Scale or the Gray Scale for Evaluating Staining.

Standards:
Dyed on worsted wool yarn: Class 1. 1% Alizaring yellow R
(2243-76-7] (CI 14030): Class 3. 1% Naphthochrome Violet R [7452-
51-9](43565); and Class 5.1% Acid Alizarine Violet N [2092-55-9](CI
15670).
Water Tests (AATCC 105-1975, ANSI L14.149-1973; AATCC
106-1975, ANSI L 14.150-1973; AATCC 107-1975, ANSI L14.151-
1973): Tests in fresh, sea, and chlorinated pool water are designed to
measure the resistance in each of dyed printed, or otherwise coloured
textile yarns and fabrics of all kinds.

Procedure:
Distilled or demineralized water are artificial seawater are used
because of the variables encountered in tap water or natural
seawater. Seawater solution is made up of 30 g sodium chloride
and 5 g magnesium chloride pool water solution is made up of 5
parts of 1% soln of available chlorine per 10.000 parts of distilled
2water (5ppm), adjusted to pH 8 with either sodium bicarbonate or
acetic acid. Specimens for each type of water test are backed with
multifiber test cloth.

For freshwater and seawater tests, the specimens are wet out in the
suitable solution for 15 min, placed in the AATCC Prespiration Tester or
Perspirometer at 69 kPa (10psi) and placed in an oven at 38oC for 18h,
after which the specimens are removed and dried at room temperature
without pressing.

162
Specimens for chlorinated-pool-water-tests are kept in 200 mL of
solution at 27o C in a closed jar for 4 h, during, which time they are
occasionally gently agitated. They are then placed in the Perspirometer
and kept at 38o for 2 h.

EVALUATION AND CLASSIFICATION:


All three water tests are graded for colour change by comparison
with the Gray Scale for Evaluating Change in Colour; either the AATCC
Chromatic Transference Scale or the Gray Scale Evaluating Staining is
used for rating the staining of the multifiber test cloth.
Water Spotting (AATCC 104-19756) (ANSI L 14.148-1963/R-
1963/R-1969):
This simple test indicates the fastness of textiles to water spotting.
It does not show whether or not the discolouration is removable.

Procedure and Evaluation:


A coloured swatch is spotted with water. The colour change is
evaluated after 2 min, and again after drying, using the Gray Scale
for Evaluating Change in Colour.

APPLICATION PROPERTIES:
Recently the AATCC has initiated a research program to develop
test methods for the evaluation of application properties of dyes in
dyeing processes. So far, three such test methods have been published
and others are to follow shortly.

Compatibility of Basic Dyes for Acrylic Fibers (AATCC 141-1976):


This test is intended of determine the behaviour of a basic dye
concerning compatibility when applied to acrylic fibers in the presence
of other basic dyes. Compatible dyes according to this definition are
those that exhaust at same rate as the other dyes in the combination.

Procedure:
The compatibility is determined is a so-called dip test where the
dye under test is exhausted on several pieces of acrylic material in
separate combinations with five basic dyes of established

163
compatibility value. There are separate yellow and blue scales
(AATCC) of five standard dyes each.

EVALUATION:
The compatibility value of the dye under test is that of the
standard dye with which is produces on-tone dyeings throughout the
sequence of dyeings. The compatibility value C ranges from 1 to 5 with
half steps.

Dispersibility of Disperse Dyes:


Filter Test (AATCC 146-1976): This test determines the
dispersibility of disperse dyes as evaluated by filtering time in filter
residue under standard conditions in aqueous media.

Procedure:
Dye powder (2g of standard and sample) is pasted with 180ml
water at 43-49o C. The pH is adjusted as shown in Table 8 and the
volume brought to 200 ml. The dispersion is heated to 71o C and
filtered it in warmed Buchner funeral through filter paper (as
indicated in Table 9), under vacuum. The time it takes for the
dispersion to pass through the filter is recorded. The filter paper is
dried for evaluation.

EVALUATION:
The residue on the filter paper is evaluated visually against the
Filter Residue Scale from 5 to 1 (AATCC).
The results are rated according to filtering time as follows:

Class Filtering time, s


A 0-24
B 25-49
C 50-74
D 75-120
E >120

164
The type of test, the filtering-time class and the residue class are
reported.
TABLE: 8
SELECTION OF APPLICABLE TEST
Tes Whatman Application of pH of
t Filter dyes dispersion
combination
I # 2 over # 4 Package dyeing of 4.5-5.0
polyester
II # 4 over # 4 Beck dyeing of 4.5-5.0
polyester
III # 4 over # 4 Dyeing of nylon 7.0-10.0
carpet and apparel

Dyestuff Migration (AATCC 140-1976):


The purpose of the test is to evaluate particulate migration of dyes
that have been padded on a textile fabric during drying as well as the
influence of auxiliaries on the migration. Such migration cab is
substantial cause of unlevelness.

Procedure:
The dye under test alone or together with auxiliaries is padded in a
concentration desired on a 5 cm X 30 cm swatch of fabric. The
swatch is immediately placed on a horizontal glass plate. A 9 cm
dia watch glass is place on a portion of the fabric. The fabric is
dried at room temperature and watch glass is removed.

EVALUATION:
The degree of particular migration is estimated by comparison of
the dye concentration in the area of fabric, which was covered by the
watch glass to the dye concentration in the rest of the fabric. Three
methods of evaluation are possible: (1) visual, by reference to the Gray
Scale for Evaluating Change in Colour; (2) by reflectance measurement
and calculation of colour difference; and (3) by quantitative extraction of
the dye from disks of fabric of equal size from the covered and
uncovered areas. Percent particulate migration (Mp) is calculated as
follows:
165
(1 – AA)
M p = 100 ------------------
ABB

Where AA is the absorbance at the analytical wavelength of the extract


from the covered area. AB is the absorbance at the analytical wavelength
B

of the extract from the uncovered area.

166
REFERENCE
1. Technical manual of American Associatio0n of Textile Chemist &
Colourist (AATCC).

2. The Chemistry of Synthetic Dyes by Venkataraman Academic


Press London.

3. Waston E.R Colour in relation to Chemical Constitution,


Longman Green London.

4. Fundamental of the chemistry and Application of dyes By P.Rys


& H. Zolinger Wiley – Inter Science London.

5. P.F Gordon, Organic Chemistry in Colour, Springer – Verlag,


New York.

6. K. Mac Laren, the Colour Science of Dyes & Pigments Adam


Hilger, Bristol.

7. A Glimpes on the experimental Textile Laboratory, Mahajan


Brothers Ahmedabad India.

8. The Colour Index, Society of Dyes & Colourist Bradford.

9. Colour Chemistry, Synthesis Properties & Application of Organic


dyes and Pigments 2nd edn, VCH, New York.

10. Colourant and Auxiliaries Vol-1 J.Shore Society of Dyers &


Colourist Bradford.

11. Kirk – Orthmer Encyclopedia of Chemical Technology, John


Wiley, New York.

12. The Chemistry of Polymers, J.W. Nicholson The Royal Society of


Chemistry Cambridg.
167