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Textile Dyes by Mansoor Iqbal
Textile Dyes by Mansoor Iqbal
DYES
By
Mansoor Iqbal
M.Sc (Applied Chemistry)
Senior Research Associate, Textile
PCSIR Laboratories complex Karachi
Ministry of Science & Technology
Government of Pakistan.
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 readers 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.
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
(1-6)
Chapter # 2
HISTORY OF DYESTUFFS
Chapter # 3
CLASSIFICATION OF DYES
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
(7-21)
(22-46)
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
Chapter # 5
REACTIVE DYES
(63-86)
DIRECT DYES
(87-91)
Direct dyes
Chemical constitution of direct dyes
Classification according to dyeing behavior
Class A
Class B
Class C
(92-100)
Azo Dyes
Anthraquinone Disperse Dyes
Miscellaneous Disperse Dyes
Methine or Styryl Dyes
Quinphthalone dyes
Coumarin Dyes
Chapter # 8
VAT DYES
Indigoid Dyes
Thioindigoid Dyes
Anthraquinone Vat Dyes
(101-109)
Chapter # 9
SULPHUR DYES
(110-116)
(117-123)
Chapter # 11
(127-142)
(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)
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
(complementary
colour)
Yellow Green
Yellow
Orange
Red
Purple
Violet
Blue
Green blue
Blue green
absorbed ()
4000 4350
4350 4800
4800 4900
4900 5000
5000 5600
5600 5800
5800 5950
5950 6050
6050 7500
Violet
Blue
Green blue
Blue green
Green
Yellow green
Yellow
Orange
Red
0
0
-N=N-
N
0
Azo
O
Nitroso
P-Quinad
O-Quinad
C=O
Ethylene
Carbonyl
O
||
CH3 C CH3
O O
|| ||
CH3 C C CH3
O O
|| ||
CH3 C CH3 C CH3
C=NAzomethine
Acetone
Colourless
Biacetyl
Yellow
Acetonyl
Acetone
Colourless
NH2
Amino
NR NR2
Alkylated
Amines
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.
C6H5 N = N C6H5
Azobenzene
H2
C6H5 NH NH C6H5
Hydrazobenzene
Indigo Blue
Indigo white (colourless)
Oxidation
Sometimes reduction completely decomposes the coloured
compound, such reduction products are called Leuco compounds.
4
H3 C
H3
H3
H3
H3
H3
H3 C
H3
C
H2 C
CCH=CHC=CHCH=CHC=CHCH=CHCH=CCH=CHCH=CCH=CHC
H
H2 C
H2
H2
H2
H3 CC
-CAROTENE
H2
History of Dyestuff
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 (GriesheiElektron,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 largescale 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
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
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 Websters
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
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
dyers 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 citys 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). Its 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
21
Classification of Dyes
OH
OH
OH
NO2
NO2
NO2
PICRIC ACID
HO3S
NO2
NO2
NO2
MARITUS YELLOW
NAPHTHOL YELLOW S
HNO2 + HCl
A PRIMARY
AROMATIC AMINE
N2Cl + 2H2 O
A DIAZONIUM
COMPOUND
N Cl + H
OH(-NH2,-NR2)
A DIAZONIUM
COMPOUND
OH(-NH2,
-NR2)
-HCl
N=N
A PHENOL,
NAPHTHOL or
AMINE
A DYE
N2Cl
NH3
N=N
BENZENEDIAZONIUM
CHLORIDE
NH2 + HCl
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)
N2Cl + H
CH3
CH3
Benzenediazonium
Chloride
CH3
N=N
CH3
N,N-Dimethylaniline
Butter
Yellow
(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 mphenylenediamine.
NH2
+
NH2
NH2
N2Cl + H
Benzenediazonium
Chloride
N =N
m-phenylediamine
NH2 + HCl
Chrysoidine
(2,4-diaminoazobenzene)
+ N2Cl
CH3
CH3
HO3S
N,N-methylaniline
N=N
CH3
NaOH
CH3
Helianthine
NaO3S
N=N
CH3
CH3
Methyl Orange
24
p-Quinoid
Chromophore
N=N
CH3
CH3
H+
OH
O3S
+
N CH3
CH3
NH N
Red
Acidic Solution
Yellow
(Alkaline Solution)
HO3S
+ -
HO3S
N2Cl + H
HO
OH
Diazotised
Sulphanilic Acid
+ HCl
N=N
Orange 2
-Naphthol
O2N
O2N
N2Cl + H
-Nitobenzene
diazonium Chloride
N=N
OH
OH
Para Red
-Naphthol
25
HCl
HO3S
N2Cl
OH
+H
OH
Reaoroinol
Diazolised
Sulphanilic acid
N=N
HO3S
OH + HCl
Reaoroinol Yellow
N2Cl + H
-Nitrobenzenediazonium
Chloride
CH2CH3
CH2CH2OH
N-Ethyl-N-( -hydroxyethyl)aniline
O2N
N=N
CH2CH3
CH2CH2OH
HCl
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
-+
+
N2Cl +
+ Cl N2
SO3H
Tetrazotised Benzidine
SO3H
Naphthionic
Acid
NH2
NH2
N=N
N= N
+2HCl
Congo Red
SO3H
SO3H
(3)
Diphenlymethane Dyes:
Auramine O: It is one of the most valuable of the
diphenylmethane dyes. It is obtained by heating Michlers ketone with
ammonium chloride and zinc chloride at 160oC.
O
ZnCl2
(CH3)2
N (CH3)2+ NH4Cl
MICHLERS KETONE
NH3
(CH3)2N
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
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
C==O
Benzaldehyde
N (CH 3)2
N (CH 3)2
N (CH 3)2
N (CH 3)2
N,N-Dimethyle aniline
N(CH3)2
N(CH3)2
HCl
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
C
H2N
H
H +
H
NH2
NH2
3[O]
OH
NH2
-2H2O
Colourless carbinol
Aniline
p-toludine
NH2
H2N
HCl
NH2
C
H2N
-H2O
Cl
NH2
PARAROSANILINE
H2N
H
H +
H
NH2
NH2
3[O]
OH
NH2
-2H2O
H
p-toludine
Colourless carbinol
CH3
O-Toluidine
CH3
+
HCl
-H2O
NH2
H2N
NH2
H2N
C
NH2
CH3
PARAROSANILINE
29
Cl
POCl3
+ H
(NCH3)2
or COCl2
N,N-DIMETHYLE ANALINE
N(CH3)2
MICHLERS KETONE
N(CH3)2
CRYSTAL VIOLET
Cl
30
OH
HO
OH
H
OH
OH
H
O
C
2H2O
CH2
NaOH
C
O
ZnCl2
FLUORESCEIN
PATHALIC ANHYDRIDE
OH
COONa+
URANINE
HO
HO
Br2
C
O
C
Br
Br
OH
Br
CH3COOH
NaOH
OH
C
O
Br
FLUORESCEIN
Tetrabromofluricine
Br
Br
Nao
O
Br
Br
COONa+
Eosin is a
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.
EOISNE
---(C2H6)2N
OH H-O
+
N(C2H6)2 (C2H6)2N
HO H
ZnCl2
C O
C=O
N(C2H6)2
- 2H2O
HCl
O
C=O
+
PATHALIC ANHYDRIDE
(C2H6)2N
N(C2H6)2
C
COOH
RHODAMINE B
Cl
(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
O
C
ZnCl2
O
-H2O
O
C=O
CO
Phenolphthalein
(Colourless)
Phthalic Anhydride
O
C O
ONa+ + NaO
OH
H+
COONa+
+ -
HO
COONa
Sodium Salt
(Red)
Phenolphthalein
(Colourless)
H+
+
OH
NaO-
OH
O
COONa
Trisodium Salt
(Colourless)
33
ONa
CH2OH
Fermentation
+
N
H
-D-Glucose
H
OH
OH H
OH
H
OH
OH
CH2OH
H
O OH
H
H
OH
CH2
H
Indoxyl
-Link
H
O
O
C
N
C
Oxidation
CH2
C
N
H
Indoxyl
O
Indigo
(Indican)
HO
+
+
N
Aniline
HO
CH2
HaOH + NaNH2
CH2
CH2
Cl
Indoxyl
H
O2
H
N-Phenylolycine
H
O
C
N
C
C
O
H
Indigo
(Indigotin)
OH
C
H
Formaldehyde
NaHSO3
Sodium
Bisulphite
SO3Na+
An Addition
Product
- +
SO3Na
+
HO
50
70OC
N
H
O
HO
C
CH2
C
H+
H2O
CH2
H
N-Phenylglycine
35
SO3Na
NaCN
CH2 -Na2SO3
OH
O
+
N
CH2
COOH
O
CH2
Cl
COOH
Chloroacetic acid
H
Anthranilic Acid
H
N-Phenylglycine-o-carboxylic acid
OH
C
-H2O
NaOH, NaNH2,
CO2
C
COOH
H
Indoxylic acid
(unstable)
O
O2
Indigo
CH2
H
Indoxyl
(2 molecules)
+
Aniline
H2C
NH2
CH2
CH2
OH
NaOH + NaNH2
Ethylene Oxide
200 0C
H
N-Phenyl-2-hydroxyethylamine
CH2 ONa+
CH2
NNa+
(1) 300 OC
(2) 240 OC
CH
N
36
+
-ONa
H2O
OH
CH
N
Indoxyl
H (Enol form)
O
C
N
Indigo
CH2
H
Indoxyl
(Keto form)
Indigo
OH
NaOH
NH2
Anthranilic Acid
2[O]
INDIGO
C=O
N
H
Isatin
37
C
C
O O
N
H
(B)
(A)
O2
C
N
CH2
H
INDIGO
INDOXYL
From above, it follows that (A) represents the structure of indigo. This
has been confirmed by the following synthesis by Baeyer (1872).
O
O
C
PCl5
C
OH
Isatin chloride
Isatin
(Enol form)
Isatin
(Keto form)
Zn CH3COOH
O
OO
C
N
H
Cl
O2
CH2
N
N
Indigo
H
Indoxyl
(Two Molecules)
O
C
C =C
N
C =C
C
O
Trans-form
Cis-form
38
X-Ray analysis shows that mostly indigo exist in the more stable transform. 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
4
C
Br 6
C
2
C
2'
1'
C 3'
O
7'
Br
6'
5'
4'
Tyrian Purple
(6,6' - Dibromoindigo)
COOH
1. Diazotize
COOH
NH2
SH
Anthranilic
Acid
COOH
ClCH3COOH
2. H2S
CH2
Thiosalicylic
Acid
OH
O
C
O2
CH
CH2
S
S
Thioindoxyl
(Enol-Form)
HaOH
200 0C
Thioindoxyl
(Keto-Form)
THIOINDIGO
C
O
(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
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
c
o
AlCl3
OH
c
C
O
O-Benzoyl-Benzoic Acid
H2SO4
OH
H
O
Anthraquinone
40
O
SO3H
+
H2SO4
Fuming
O
Anthraquinone
O
Anthraquinone
Anthraquinone-2-sulphonic acid
SO3H
SO3Na
NaOH
O
Anthraquinone
O
Sodium salt of
anthraquinone-2-sulphonic acid
Anthraquinone-2-sulphonic acid
O
9
6
5
10
O
- +
ONa
+
-ONa
- +
SO3Na
Na2SO4
3
4
2H2O
Sodium salt of
1, 2-dihydroxyanthraquinone
ONa
O
ONa
H+
O
OH
OH
O
Alizarin
(1, 2-dihydroxyanthraquinone)
OH
OH
OH
C
O
OH
H2SO4
C
Catechol
O
Phthalic anhydride
O
Alizarin
(1,2-dihydroxyanthraquinone)
The above facts limit our choice to two structural formula for alizarin.
O
OH
O
OH
OH
OH
(A)
(B)
42
OH
OH
OH
OH
NO2
O
DIFFERENT
NO2
O
O
NO2
OH
OH
OH
OH
NO2
IDENTICAL
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
Al
OH
+
OH
Al3 + fibre
Modarant
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.
mordant dyes on fibre
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
N
C
OH
C
Reduction
Oxidation
C
N
C
C
OH
H
INDIGO COLORLESS
WATER SOLUBLE
O
H
INDIGO BLUE WATER INSOLUBLE
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
NH2
O
OH
O
CELLITON FAST PINK B
N-CH3
N-CH3
H
CELLITON FAST BLUE B
46
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
C
NH
CO
NH
H
CO
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
CH
CH2
CH2
CH
NH2
HOOC
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
NH
CH
CO
NH
CH
CO
NH
CH
CO
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
CARBOXYAMIDE
DIPHENYLE
NaO3S
NH2
CH=CH
STILBENE
HO
J-ACID
NaO3S
HC
S
CH
CH
NH2
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 3methy-1-phenylpyrazol-5-one), with the structures shown:
51
NaO3S
HO
H3C
C-CH3
S
N=N-C
CONHPh
N
H3C
CI DIRECT YELLOW 8
NaO3S
NaO3S
NHPh
N=N
N
N
HO
CI DIRECT BROWN 30
NaO3S
NH2
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 aminocontaining dyes in succession. Substitution of the first chlorine atom
52
Stage 1
N
(Dye 1)
NH2 +
Cl
Low
N
N
Temperature
Cl
Cl
N
Stage 2
(Dye 1)
Cl
NH
N
(Dye 1)
NH
N
N
(Dye 2)
Moderate
Temperature
NH2
Cl
NH
Cl
(Dye 2)
N
NH
(Dye 1)
N
N
Stage 3
NH
N
N
Cl
(Dye 2)
N
(Dye 1)
NH
N
N
(Dye 3)
NH2 High
Temperature
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
OH
N
OMe
N
COONa
NH
OH
N N
NH
N
Me
NaO3S
(1)
NHPh
O
SO3Na
COONa
N
H2N
Na
NH
N
NH-
HN
N
-N=N-
OH
S
O3
(2)
OAc
CH2
H
H
OAc
H
OAc
O
H
H
H
CH2
OAc
54
OAc
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 75o80oC, 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
CO.O.H2C.CH2.O
OC
CN
n
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.
62
Reactive Dyes
OR
C
H2N
Dye N C
H
CCl
N
ROor
HO-
OR
C
N
COR
H2N
Dye N C
H
OH
C
H2N
N
COH
N
Dye N C
H
R=Cellulose residue
63
N
COH
N
OH
HN
CCl
N=N
NaO3S
SO3Na
64
Cl
C
N
SO3Na
OH
HN
N=N
NaO3S
SO3Na
CNH2
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. Waterinsoluble 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
N=N
C .NH
Cl.C
N
NH.Ph
OH
SO3Na
NaO3S
N
C.
Cl
CuPC= (SO3H)2
SO2.NH
N
C . Cl
NH. C
N
N
C.
Cl
Which, according to B.P. 948 256 (ICI), dyes cotton a bright greenishblue of excellent fastness to wet treatments.
The blue monochlorotriazinyl dye.
O
SO3Na
HN
O
H
NC
NaO3S
N
C OPh
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- (-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:
N3
Cl
.
C4
5 C.Cl
6
Cl .C 2
C.Cl
Cl
C
F
C
N
C
F
DRIMALAN (S)
VERAFIX(FBY)
LEVAFIX(FBY)
Dye NC
H
S
C Cl
N
67
REATEX (FRAN)
Cl
SOLIDAZOL(FRAN)
N
N
Cl
Dye N C
H
REATEX(FRAN)
N
Cl
Quinoxaline derivatives:
The use of various qu8inoxaline derivatives is covfred by B.P. 995
796 (Fby):
=C
N
.X
C .X
N=
SO3H
SO3H
N=N
N
Cl.C
SO3H
CO.NH
SO3H
Cl.C
SO3H
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
O
NH2
NH2
Br2 in O - dichlorobenzene
NH
NH
O
CO.Me
CO.CH2.Br
HO3S
OH
N=N
NH2 NH.CO
Br
HO3S
SO3H
Dye.SO2CH=CH2+OCellulose Dye.SO2.CH2CH2.OCellulose
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 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
.
.
CO
CH=CH2 or a precursor such as NH.CO.CH2CH2OSO3Na. As with
NH
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 Dglucose 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 ochlorophenol. 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 C.I.
Generic
Name
Brill.
Reactive
Yellow AG Yellow 4
Yellow RG Reactive
Yello2w 7
3.
Yellow 4R
4.
Brill.
Orange 2R
Reactive
Orange 14
Reactive
Orange 14
5.
Brill. Red
EB
Reactive
Red 2
6.
Brill. Rose
3B
Reactive
Red 11
7.
Brill. Pink
B
Brill.
Magenta B
Brill. Violet
RR
Brill. Blue
R
Reactive
Red 74
Reactive
Violet 13
Reactive
Violet 14
Reactive
Blue 4
C.I.No.61
205
Reactive
Blue 9
8.
9.
10
11.
Navy Blue
3R
Constitution
Remarks Hue
Monoazo Reactive
Dichlorotriazinyl
Azo Reactive
System
Dichlorotriazinyl
Monoazo
(Pyrazolone)
Azo Reactive
System
Dichlorotriazinyl
Monoazo Reactive
System
Dichlorotriazinyl
Azo Reactive
System
Dichlorotriazinyl
Azo
Bright Reddish
yellow
Bright Reddish
Yellow
Azo
Azo
Anthraquinone
Reactive system
Dichlorotriazinyl
Bright Reddish
Orange
Bright Reddish
Orange
Bright Blush
Red
Bright Blush
Red
Bright Bluish
Pink
Bright Reddish
Violet
Bluish Violet
Bright Blue
Azo (copper
Reddish Navy
complex) Reactive
System
Dichlorotriazinyl
72
Constitution
Remark Hue
Monoazo
(pyrazolone)
Monochlorotriazinyl
Azo
Bright
Greenish
Yellow
Bright
Reddish
Yellow
Yellowish
Orange
Bright
Reddish
Orange
Reddish
Orange
Bright
Bluish Red
Bright
Bluish Red
Bright Violet
Golden
Yellow IR
Brill.
Orange R
Reactive
Orange 12
Reactive
Orange 37
Monoazo
Brill.
Orange 2R
Brill. Red
6B
Brill. Red
8B
Brill. Violet
3R
Reactive
Orange 13
Reactive Red
76
Reactive Red
31
Reactive
Violet 1
Monoazo
9.
Red Brown
4R
10. Turquoise
Blue A
11. Turquoise
Blue 2-G-X
Reactive
Brown 9
Reactive
Blue 71
Reactive
Blue 3
12. Turquoise
Blue 25
13. Navy Blue
R
Reactive
Blue 25
Reactive
Blue 59
Azo
Azo
Azo
Azo (copper
complex) Reactive
system
Monochlorotriazinyl
Monoazo(Chhromi- Bordeaum
umcomplex)
Phthalocyanine
Greenish
Blue
Phthalocyanine
Bright
Greenish
Blue
Phthalocyanine
Greenish
Blue
Azo
Reddish
Navy
73
SUMIFIX HF YELLOW 3R
SUMIFIX HF RED 2B
SUMIFIX HF BLUE BG
SUMIFIX HF NAVY 2G
SUMIFIX VS DYES:
1.
2.
3.
4.
5.
6.
76
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
6. REACTOBOND MEGENTA MB
7. REACTOBOND VIOLET C4R
8. REACTOBOND BLUE MR
9. REACTOBOND BLUE M2R
10. REACTOBOND BLUE M4GD
REACTOBOND XL DYES:
1.
2.
3.
4.
5.
6.
REACTOBOND YELLOW XL
REACTOBOND RED XL
REACTOBOND RED XL3B
REACTOBOND BLUE XL
REACTOBOND NAVY BLUE XL
REACTOBOND BLACK XL
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
LEVAFIX:
1.
2.
3.
4.
5.
6.
7.
8.
ORANGE E3GA
BRILL RED E4BA GRAIN
BRILL YELLOW E3G GRAIN
YELLOW CA GRAIN
RED CA GRAIN
BLUE CA GRAIN
NAVY CA GRAIN
RUBINE CA GRAIN
SUNFIX (CHEMDYES CORPORATION)
84
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
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
(1)
N
SO3Na
NH.CO
NH2
N N
SO3Na
NH2
NaO3S
87
(2)
H2 N
NH2
NH2
NH2
SO3Na
N=N-
N=N-
NH2
N=N-
N=N-
NH2
SO3Na
CH
CH
N=N-
OH
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
C
N
N
(7)
88
NH2
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 makers 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
91
Disperse Dyes
N=N
CH2SO3Na
H3CCOHN
N=N
CH3
C2H5
O2N
N=N
N
C2H4OH
93
H2N
N=N
NH2
OCH3
N=N
R2
C2H4OCOC2H5
R1
The dye BP 1351382 has been a bluish green dye for PE. Its structure is
as follows:
NO2
OCH3
H
N
N=N
H3CCO
C2H6OCOC2H6
H3CCOHN
94
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
Light
fastness 3 3.5
thermo
fixation 2.5 1.5
fastness
CN
4.5 7
4
7
4.5
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
N
B.P.1171803 ORANGE PE
OH
OCH3
NO2
N=N
N=N
C2H4OCOCH3
C2H4OCOCH3
OCH3
Cl
NHSO3CH3
B.P.1805326 NAVY PE
NH2
NH2
OCH3
O
HO
DURANOL RED 2B
NH2
NHCH3
NH2
OCH3
NHCH3CH2OH
N
H
NHCH3CH2OH
OH
CH2CH2OH
NHCH3CH2OH
H2N
OR
R=H , ALKYL
or COCH3
NH2
O
H
NH2
C=X
X=O or NH
N-R
C=X
NH2
97
R= ALKYLE,ALKYL ARYL
HYDROXY ALKYLE or cyano
alkyle group
By introducing phenoxy and other derivatives in 2-position of 1-amino 4hydroxyanthraquinone, it becomes possible to improve thermofixation
fastness.
NH2
R
R could be
O
OH
O
H
OH
OCH2CH2OCH3
SCH3 ,
Cl
SO3NHCH2CH2OC2H5
NH
OH
N=N
NO2
CH2CH2CH3
NH
SO2
98
N
CH2CH2CH3
COOC2H5
C2H4Cl
C2H4Cl
N
CHO+CH2CN
CH=C-CN
n-H9C4
n-H9C4
Cl
Cl
C
HC
N
C
Cl
Cl
SO2C6H5
OH O
C
N
C
O
CO
HN
+ H2N
NO2
POCl2
HN
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-hydroxybenzaldehyde and 2-cyanomethyl benzothiazole in a mixture of acetic
acid and dimethy formamide.
CHO
+
C2H5
OH
24 HOURS
H2C-C
NC
25 C
C2H5
N
C
C5H2
N
NH
C5H2
FORMAZINE DYES
These give blue disperse dyes which are suitable for nylon
O
Ni
N
C
Benzene ring has substituents such as
NHCOCH3,SO2R,SO2NR1,R2
CN
100
Vat Dyes
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
C
H
N
O
C
CH2
+ O2
C=C
N
H
N
H
2 H2O
C
O
INDIGO
INDOXYL
CH2O+
NHCH2CN
NHCH2SO2Na
NH2 NaHSO3
NaOH +H2O
O
C
fusion with
CH2
N
H
NaNH2 + NaOH+KOH
NHCH2COONa + NH3
OXIDATION
O
C
H
N
C= C
N
H
C
O
INDIGO
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 readyreduced 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
N
C
C-C
N
H
C
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
OSO3
Cu.C5H5N
2
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 45 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
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
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
O O
C
N
H
Me
N
H
NH
NH
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
109
Sulphur Dyes
N
N
S
1
2
3
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
N
H
113
114
CI Sulphur CI 53055
Brown 10
Immedial
Yellow
Brown G
(Cassella)
CI Sulphur CI 53185
Black 1
Immedial
Black AT
(Cassella)
and many
other
brands
116
phenylamino
-naphthalene1-sulphonic
acid
m-Tolyenediamine
CuSO4, then
oxidise with air
(ref. 8)
Heat with
sulphur at 210o
rising to 250oC.
Dissolve the
product in eq.
Na2S + NaOH,
heat at 240o and
evaporate (ref.
9)
2,4Heat with eq.
Dinitropheno Sodium polyl or 2,4sulphide under
dichloronitro reflux (110o
120o C), dillute
-benzene
and oxidise with
air (ref. 10)
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 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)
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
(b)
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)
(d)
120
(e)
(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)
123
11
126
12
Banned Amines
Q.1
Q.2
Q.3
Q.4
Q.5
Q1.
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
Formaldehyde
Toxic pesticides
Pentachlorophenol (PCP)
Heavy metal traces
Azo dyes which release carcinogenic amines
Halogen carriers
Chlorine Bleaching
Formaldehyde
(i) Baby Clothing 20
(ii) Close to skin 75
(iii) Outer wear 300
20
75
300
20
75
300
50
300
500
Toxic Pesticides 1
5
1
1
Pentachlorophenol 0.5
-0.5
Ban
Heavy Metals
(i) Arsenic
0.001 to 0.01
(ii) Lead
0.004 to 0.04
(iii) Cadmium
0.0005 to 0.005
(iv) Mercury
0.0001 to 0.1
(v) Copper
0.3 to 100.0
(vi) Chromium
1 to 20
(vii) Cobalt
2 to 20
(viii) Zinc
0.5 to 5.0
(ix) Nickel
0.02 to 10.0
Azo dyes
Ban BanBan Ban
containing
carcinogenic
amines
Halogen Carriers Ban --- --- Ban
Chlorine
___ ___ ___ To avoid
Bleaching
Q3.
20
75
300
Indian
Eco
Label
20
75
300
0.1 to 1
1
0.05 to 0.5 0.5
10.0
(for all
heavy
metals)
Ban
50.0
Ban
Ban
200.0
___
CI Generic Name
Acid Orange 45
Acid Red 85
Acid Black 29
Acid Black 94
Azoic Diazo Compo.112
Direct Yellow 1
Direct Yellow 24
Direct Orange 1
Direct Orange 8
Direct Red 1
Direct Red 10
Direct Red 13
Direct Red 17
Direct Red 28
Direct Red 37
Direct Red 44
Direct Violet 1
Direct Violet 12
132
CI Constn. No.
22195
22245
30336
37225
22250
22010
22370
22130
22310
22145
22153
22150
22120
22240
22500
22570
22550
19.
20.
21.
22
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
Direct Violet 22
Direct Blue 2
Direct Blue 6
Direct Green 1
Direct Green 6
Direct Green 8
Direct Green 8:1
Direct Brown 1
Direct Brown 1:2
Direct Brown 2
Direct Brown 6
Direct Brown 25
Direct Brown 27
Direct Brown 31
Direct Brown 33
Direct Brown 51
Direct Brown 59
Direct Brown 79
Direct Brown 95
Direct Brown 101
Direct Brown 154
Direct Black 4
Direct Black 29
Direct Black 38
22480
22590
22610
30280
30295
30315
-30045
30110
22311
30140
36030
31725
35660
35520
31710
22345
30056
30145
31740
30120
30245
22580
30235
CI Generic Name
Acid Red 4
Acid Red 5
Acid Red 24
Acid Red 26
Acid Red 73
CI Constn. No.
14710
14905
16140
16150
27290
133
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
23635
27200
26660
24125
26665
27190
20530
-18133
18129
-18075
------21010
76035
23660
23375
23380
23370
29173
23500
24100
23560
23565
29185
29190
23630
23050
29175
23505
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
Direct Red 72
Direct Violet 21
Direct Blue 1
Direct Blue 3
Direct Blue 8
Direct Blue 9
Direct Blue 10
Direct Blue 14
Direct Blue 15
Direct Blue 22
Direct Blue 25
Direct Blue 35
Direct Blue 53
Direct Blue 76
Direct Blue 151
Direct Blue 160
Direct Blue 173
Direct Blue 192
Direct Blue 201
Direct Blue 215
Direct Blue 295
Direct Green 85
Direct Blue 222
Direct Black 91
Direct Black 154
Disperse Yellow 7
Disperse Yellow 23
Disperse Yellow 56
Disperse Orange 149
Disperse Red 151
29200
23520
24410
23705
24140
24155
24340
23850
24400
24280
23790
24145
23860
24411
24175
----24115
23820
30387
30368
30400
-26090
26070
--26130
135
1.
1.1
1.2
1.3
1.4
1.5
A
S. #
1
1.
2.
3.
4.
5.
6.
10.0
0.5
7.
150
Below
detectable
limit
10.0
10.0
0.5
0.5
(Detectable
limit using
GC.MS)
150
150
200
200
200
1.0
1.0
1.0
Nil
pH of aqueous extract
Coupled Amines released
from Azo-dyes (Sum
parameters)***
4.0-7.5
50
Nil
Nil
(Below
detectable
limit)
4.0-7.5
4.0-7.5
50
50
(Detectable
limit using
GC-MS)
8.
9.
10.
11.
12.
137
B.
S. #
1
1.
2.
3.
4.
5.
6.
7.
3.
4.
5.
6.
7.
pH of aqueous extract
Coupled Amines released
from Azo-dyes (Sum
parameters)***
4.0-7.5
50
(Below
detectable
limit)
4.0-7.5
4.0-7.5
50
50
(Detectable
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
Dalapon
FUNGICIDES:
Carbendazim
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
APPENDIX-B
Coupled Amines released from Azo dyes
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
18.
19.
20.
21.
22.
4-Aminodiphenyl
2-Amino-1-nitrotoluene
Benzidine
4-Chloro-o-toluidine
2-Naphthylamine
O-Aminoazotoluene
p-Chloraniline
2, 4-Diaminoanisole
4, 4-Diaminodiphenylmethane
3, 3-Dichlorobenzidine
3, 3-Dimethoxy-benzidine
3, 3-Dimethylbenzidine
3, 3-Dimethyl-4, 4-diaminodiphenylmethane
P-kresidin (2-Methoxy 5-methylaniline)
4, 4-Methylene-bis-(2-chloraniline)
4, 4-Oxydianiline
4, 4-Thiodianiline
0-Toluidine
2, 4-Toluyendiamine
2, 4, 5-Trimethylaniline
p-Amino-azobenzene
2-Methoxyaniline
142
13
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
144
I
0.01
I
0.1
III
0.2
IV
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
Classification
I
4
I
4-3
III
3
IV
3-2
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
/ L H2Oa,b
0.5
2.0
pH, initial
9.0-9.5
10.5
146
10.5
0.5
10.5
Table 3 Cont.
Test Conditions
Wool, I Silk,
II
2
1
20:1
30:1
Time, h
liquor / cloth
ration
Distrilled water.
Doubly sulfonate coaster oil.
Cotton,
III
2
30:1
Cotton,
IV
1
1:1
Temp. o
C
32
38
43
Soap conc,
wt%
3.75
3.75
3.75
Na2CO3
conc, wt%
1.5
1.5
1.5
Time, h
0.5
1.5
4.5
150
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
205 + 2
V
219 + 2
VI
ISO
150 + 2
I
180 + 2
II
210 + 2
III
2.
3.
Class
1
2
2-3
3
3-4
4
4-5
5
5-6
6
6-7
7
7-8
L8
L9
L9
L8
L9
8
8-9
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.
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 1291975):
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
o
volume mL
No.
C
IA
IIA
IIIA
IVA
40
49
71
71
200
150
50
50
Detergent
of Total
volume,%
0.5
0.2
0.2
0.2
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 homemachine 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
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
Time,
min
5
10
Temperature,
oC
108
115
Pressure,
kPa
34
69
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
Standards:
Dyed on worsted wool yarn: Class 1. 1% Alizaring yellow R
(2243-76-7] (CI 14030): Class 3. 1% Naphthochrome Violet R [745251-9](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 L14.1511973): 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
Filtering time, s
0-24
25-49
50-74
75-120
>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
dyes
dispersion
Filter
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 -----------------AB
Where AA is the absorbance at the analytical wavelength of the extract
from the covered area. AB is the absorbance at the analytical wavelength
of the extract from the uncovered area.
B
166
REFERENCE
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