History of Dyestuff 2

The historical development of the synthetic dyestuffs dates back to

1856, when eighteen year old, W.H. Perkin discovered the synthesis of
Mauveine, a basic dye, by accident, while he was engaged in the study of
the action of potassium dichromate on aniline sulphate. He successfully
converted the process he had developed in laboratory to a large-scale
production, and demonstrated the application of the dye on silk. The
intermediates nitrobenzene and aniline required in the production were
also made commercially by him. Nitrobenzene was earlier prepared by
Mansfield in 1847.
This historical discovery of the first synthetic dye was followed by
the syntheses of numerous dyestuffs made for the first time in their
laboratories by the individuals or the group of scientists putting in
constant efforts and getting due credit for their discoveries. Earlier
discoveries worth mentioning include the synthesis of Magenta, a basic
dye (Verguin, 1859), Aniline blue, a basic dye (Girard and de Laire,
1860), Aurine, a basic dye (Runge and then Kolbe and Schmitt, 1861),
Methyl Violet, a basic dye (Bardy, 1866), Induline, a basic dye (Dale and
Caro, 1863), Bismark Brown, an azo dye (Martius, 1863), Aniline Black,
an ingrain dye (Light foot, 1963) Alizarin, an anthraquinone dye (Graebe
and Libermann, 1868), Fluorescein, a basic dye (Bayer, 1871), Eosin, a
basic dye (Caro, 1871) Orange II and Orange IV, azo dyes, (Roussin,
1876,) Methylene Blue, a basic dye (Caro, 1876), Malachite Green, a
basic dye (O’Fischer, 1877), Indigo, an indigoid vat dye (Bayer, 1880),
Para red, an azo dye (Read, Holiday and Sons, 1880), Crystal Violet, a
basic dye (Kern, 1883), Auramine, a basic dye (Kern, 1883), Congo Red,
an azo dye (Boettiger, 1884), Tartrazine, an azo dye (Ziegler, 1884),
Indigo, an indigoid vat dye by newer syntheses (Heumann, 1890 and
Sandmeyer, 1899), Indanthrene blue, a vat dye (Bohn, 1901), Benzo fast
scarlet 4 BS, an azo dye (Israel and Kolthe, 1900), Indanthrene Dark
Blue BO, Green B, and Black BB, vat dyes (Bally and Isler, 1904),
Indanthrene Golden Orange G, a vat dye (Scholl, 1905), Indanthrene
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Brown GR, olive R and Khaki GG, vat dyes (MLB, 1908 to 1911),
Indanthrene violet RN, Red BN and Red Violet RRN, vat dyes (Ullmann
and coworkers, 1909 and 1910), Hydron Blue R, a sulphurised vat dye
(Hass, 1908), Naphtol AS, a coupling component for azoics (Grieshei-
Elektron,1912), Alizarin Direct Blue A, an anthraquinone dye (Herzberg
1913) and Brilliant take colours from basic dyes (BASF, 1913) and
Brilliant lake colours from basic dyes (BASF, 1913). All these
discoveries required requisite intermediates for the production as large-
scale ventures and the technology for the production of the intermediates
suitable for the dyes was naturally made available. These discoveries
were made before the First World War (1914 to 1918) and until about
1920, as the effect of the war, the progress of chemical industry became
stagnent.
All the discoveries made during the period mentioned above (1856
– 1914) came into picture as a result of certain other auxiliary discoveries
made and certain important theoretical suggestions initiated by pioneers
of organic chemistry. There is a likelihood that as an error, the invaluable
work of many individuals and organizations might not have been
recorded Griess discovered diazotisation in 1858 and the coupling of
diazonium salts subsequently in 1864 and his work is so valuable even
today, that based on his discoveries, the azo dyes were developed and
today they cover partically half the quantum of the total quantity of
dyestuffs under commercial use. All the chemists, including the colour
chemists are also indebted to the grand services rendered by Kekule in
the field of organic chemistry by suggesting his institutional benzene and
allied aromatic hydrocarbons. A large number of organic reactions were
investigated by various scientists during the period and nitration,
sulphonation, oxidation, reduction, alkylation, quaternization, alkali
fusion, thionation etc., were developed probably without the sufficient
background of the knowledge of organic chemistry since the exact nature
of an the action of variety of reagents was not well established. The study
of the correlation of colour and chemical nature of the compounds had
been attempted which no doubt helped many other scientists to choose
the right tracks. The discoveries of the organic compounds like
Bnaphthol H-acid J-acid, Primuline Base, various anthraquinone
derivatives, etc., worked as intermediates and led to the discoveries of
then novel dyestuffs which are popular even today.
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 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
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which a lot of efforts were made to introduce newer products for
colouration of textile fibres. With the result, a great number of new
members in already established classes of dyes such as direct cotton
dyes, acid dyes, vat dyes, etc. were introduced. Newer series of dyes for
cellulose acetates fibre were also discovered. Pigment emulsion
techniques for printing of textile materials were developed. Optical
brighteners for whitening of textile fibres were introduced in the market
in 1940.
The first firm, Arlabs, manufacturing dyestuffs and allied products
in India, began in 1940 and various firms made further progress of
manufacturing various intermediates and dyes in India after the
independence.
With the discoveries and exploitation of newer synthetic fibres
such as polyester and polyamide, it became necessary to design new
structures of dyestuffs, which could suit the dyeing of these hydrophobic
fibres. There was a revival of interest to check the suitability of earlier
known dyes for these fibres also, for example, acid dyes were applicable
to the polyamide fibre and the series of metal complex dyes were brought
in the field. The dyestuffs suitable for cellulose acetate were found to be
applicable to polyester. However, they being inferior to this fibre due to
its compact structure, it was necessary to modify the original cellulose
acetate dyes from their fastness and dyeing character point of view.
Various newer techniques were developed in the application of the
dyestuffs on polyester and in one of such developments, the application
of the insoluble dyes in the form of microfine disperions called as
disperse dyes were brought into commercial practice which is being
followed even today.
The first reactive dye, the dye which reacts with the fibre during
dyeing process forming a chemical covalent bond with the fibre structure
as against the conventional dyes which are physically bound to the fibre
structure, was discovered by Rattee and coworkers of ICI in a sensational
way, while examining the dyeing character of certain dyes containing
active chlorine attached to triazine ring, and earlier known to give fast
dyeing especially to washing on cotton. A reactive dye after dyeing by a
suitable method remains attached to the fibre because of chemical
bondage and its washing fastness is of high standard. After a series of
triazinyl class of reactive dyes was introduced by ICI, many dyestuff
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firms concentrated their research and development investigating novel
systems for the production of reactive dyes. Dyestuffs containing several
groups of reactive systems were patented and few of them were
commercially exploited. Hoechst introduced B-sulphato ethyl sulphone
called as vinyl sulphone reactive dyes, which were superior in their
dyeing properties to triazine class.
The progress was constantly made in the fields of pigments,
fluorescent brighteners, and azo dyes from novel diazonium salts, etc, as
a result of the advancements in the chemistry of heterocyclic compounds.
The introduction of heterocyclic moities in the dyestuff structures
modifies their property in many ways. Smaller heterocyclic systems can
restrict the molecular weight of the dye changing its dyeing character,
certain heterocyclic systems effect the shift of the absorption maximum
of wavelength to higher wavelength in the visible range of spectrum,
generally most of the heterocyclic systems in dyestuff help to increase
the fastness properties such as sublimation fastness in disperse dyes. A
pouring number of patents were filed worldwide on the subject,
exploiting usage of many heterocyclic systems.
With the advances in newer analytical techniques such as visible,
ultra violet and infrared spectra, it became possible to detect the
properties of dyes. Newer tools in modern organic chemistry such as
Nuclear Magnetic Resonance and Mass Spectra surpassed all the
conventional methods of elucidating the structure of complex organic
molecules. Chromatographic methods helped to separate various
dyestuffs from their isomers, etc. These techniques and the overall
growth of the technology and chemical engineering sciences made it
possible for the colour chemists to broaden their ideas and grow fast.
With the advent in the polymer chemistry, newer polymers such as
plastic materials and fibres were put into the market. Polypropylene and
polyacrylic fibres are important discoveries for a colour chemist.
Polypropylene finds industrial and restricted domestic applications.
Polyacrylic commonly known as PAN Polyacrylonitrile fibre has
partially replaced wool because of the matching of its properties with
other synthetic fibres especially polyester required for obtaining the
blends. The dyestuffs were synthesised by examining the properties and
characteristic groupings or side chains is quite adament to known dyes
for the synthetic hydrophobic fibre polhyester, and therefore, special
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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
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by organised sectors as well as small scale industries which took a bold
step in making larger quantity and better quality of variety of products
which are direct requirements for dyestuff industries. The export market
possibilities in the recent years have also increased the horizon of many
ambitious dyestuff firms to enter in the worldwide competition in the
dyestuffs and intermediates.
The main threatening problem in the industrial world facing today
and applicable to dyestuff field is the pollution problem. The dyestuff
industrial waste in the form of atmospheric gases and wastewaters
pollutes the neighbouring area. The handling of hazardous chemicals like
solvents, cyanides, lead salts, mercury salts, etc, which are often required
in the dyestuffs and their intermediates production is posing problems.
The handling and production of carcinogenic intermediates regularly
involved in the production, such as benzidine and its derivatives, a- and
B-napthylamines, diphenylamine, etc., has created setbacks. For the
pollution control, newer techniques have been introduced and are further
being developed by absorbing the Industrial gases and giving appropriate
treatments to waste waters to minimise pollution. An exaustive study has
been made on careful handling of solvents, chyanides, etc. The processes
where lead salts, mercury salts, etc., were essential are abondoned or
replaced by new safer methods. These developments are notable from
ecology point of view. Benzidine and its derivatives are important for the
production of many dyestuffs consumed in huge quantities, however,
because of the carcinogenic nature of these intermediates they are being
banned all over the world and are being replaced by new comparatively
much safer diamines. The use of β-nahthylamine for making its
derivatives is no more in practice, the methods are abondoned or
modified by using a much safer sulphonic acid, Tobias acid (β-
naphthylamine – &-sulphonic acid). Many such examples can be cited in
the dyestuff chemistry.
It is rightly said that the development made in any field has to face
major setbacks. It is hoped that the future development of intermediates
and dyes to be exploited commercially will be thoroughly investigated
first from the point of view of ecology and safety of human beings and
animal as well as plant kingdom.
Ever since primitive people could create, they have been
endeavoring to add color to the world around them. They used natural
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matter to stain hides, decorate shells and feathers, and paint their story on
the walls of ancient caves. Scientists have been able to date the black,
white, yellow and reddish pigments made from ochre used by primitive
man in cave paintings to over 15,000 BCE. With the development of
fixed settlements and agriculture around 7,000-2,000 BCE man began to
produce and use textiles, and would therefore add color to them as well.
Although scientists have not yet been able to pinpoint an exact time
where adding color to fibers first came into practice, dye analysis on
textile fragments excavated from archaeological sites in Denmark have
placed the use of the blue dye woad along with an as yet unidentified red
dye in the first centuryCE.
In order to understand the art and history of dyeing, we must first
understand the process of dyeing itself. According to Webster’s
dictionary, dyeing is “the process of coloring fibers, yarns or fabrics by
using a liquid containing coloring matter for imparting a particular hue to
a substance.” There are three basic methods of “imparting a particular
hue” to a substance. The first is by staining an item, a temporary means
of coloration where the color is rubbed or soaked into an item without
the benefit of some sort of chemical fixative to preserve the color. The
next is the use of pigmentation, wherein the color is fixed to the surface
of an object by another adhesive medium. A true dye is when the color of
a substance is deposited on another substance in an insoluble form from a
solution containing the colorant.
Natural dyes can be broken down into two categories: substantive
and adjective. Substantive or direct dyes become chemically fixed to the
fiber without the aid of any other chemicals or additives, such as indigo
or certain lichens. Adjective dyes, or mordant dyes, require some sort of
substance, (usually a metal salt) to prevent the color from washing or
light bleaching out. Most natural dyes are adjective dyes, and do require
the application of a mordant (the metal salt) solution to the fibers at some
point in the dyeing process. Aluminum and iron salts were the most
common traditional mordants, with copper, tin and chrome coming into
use much later. In rural areas where these metals were not widely
available, plants were also used as mordants, especially those that have a
natural ability to extract such minerals from the earth, such as club moss.
Most ancient and medieval dyers mordanted their yarns and fabrics
before dyeing them. Alum and Iron were used as mordants in Egypt,
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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
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significant economic impact on the industry as they produced a coarser
quality of fabric than the imported fabric, and therefore had difficulty in
obtaining a good supply of cotton fiber.
Scientists are almost certain that dyeing was practiced throughout
the world, but it is difficult to obtain proof on this for two reasons. First,
not all cultures left written records of their practices. Second, because of
the wide variance of environmental conditions and degree of geological
disturbance, it is not easy to find well-preserved evidence of dyed textiles
in many archaeological sites. A Chinese text from 3,000 BCE lists dye
recipes to obtain red, black and yellow on silks. Ancient Indian texts
describe several different yellow dyestuffs, how to obtain reds from the
wood and bark of certain trees, and also notes the use of indigo to create
blues on cotton. In Central and South America they dyed bast fibers
(plant fibers) in shades of red and purple with the bodies of the cochineal
insects (Dactylopius coccus).
A Greek artifact known as the Stockholm Papyrus details
dyestuffs and techniques in almost a recipe fashion as it was practiced
Egypt in the third and fourth centuries CE. The great detail in which the
preparation of the fibers and the dyeing materials and the dyeing process
itself are recorded has led scholars to believe that it had to have been
practiced for thousands of years previously in order to raise the process
to such a science and art. It discusses mordanting the fibers using alum,
copper and iron oxides to darken or “sadden” the red, blue, green and
purple dyes, as well as the occasional use of tin and zinc. It describes
over ten different recipes for using alkanet (Anchusa tinctoria) root as a
dye employing camel and sheep urine, lentils, vinegar, wild cucumber
and barley malt among others as aids to producing color. It also gave
recipes on obtaining purple hues by overdyeing the alkanet with woad
(Isatis tinctoria), madder (Rubia tinctorum), kermes (made from the dried
bodies of the female shield louse or scale insect (Kermes ilicis)) and the
heliotrope plant (Heliotropium arborescens). Excavated coptic textiles
dating from the fourth to the sixth century CE show use of weld (Reseda
luteola) to produce yellow, madder and woad for dark purple, and blue
from indigo (Indigofera tinctoria). Scientists have been able to date a red
obtained from Egyptian madder root from the fourteenth century BCE.
In the Mediterranean before the advent of Christianity, a whole dyeing
industry arose around Tyrian purple. Tyrian purple is produced from the
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mucous gland adjacent to the respiratory cavity within some species of
Purpura and Murex species of shellfish. The shells were crushed to
extract this fluid, which only turns purple once it has been applied to the
fiber and exposed to light and oxidation with the air. The Phoenicians,
skillful shipbuilders and sailors that they were, scoured the coastlines for
sight of these whelk shells, and established a dyeworks and trading
station wherever they found a plentiful population of these shellfish.
Coastal Indians of Mexico were also using shellfish, but their delicate
method involved blowing and tickling the shellfish to get them to spit out
the dye precursor directly onto the cotton fibers. Even Ireland can
produce archaeological evidence of dyeing with the native dog-whelk
shells in the seventh century CE. Both Discorides, the Greek physician
and Pliny the Elder, the Roman naturalist, mention in their first century
works the preparation and dyeing of wool with various shellfish to
produce colors of red, blue, purple and violet after first being mordanted
with soapwort (Saponaria officinalis), oxgall or alum. (Schetky, 4) Both
authors also mention the use of Indigo from the Orient to obtain blues,
and Herodotus describes its use in a 450 BCE text. Dioscorides also
mentions other dye plants of the ancient world, including madder, saffron
(Crocus sativus) and weld for yellow, and woad for blue. Walnut shells
(Juglans nigra), oak bark (Quercus sp.), pomegranate flowers (Punica
granatum) and broom (Genista tinctoria) were also used in conjunction
with various mordants; but galls formed on trees could mordant
themselves, being high in tannic acid.
In Europe the art of dyeing rose to new heights with the diversity
of climate, culture and migration/invasion waves. This was further
influenced by the direct impact of trade instigated by the Crusades and
furthered by the growing cultural awareness of the Renaissance period -
everyone in Europe wanted the exotic, colorful dyestuffs from the Orient,
and later from the Americas. Caravans of camels would cross the Gobi
desert for centuries bringing goods from China to the Mediterranean. By
the 12th century the two main trade routes for imported dyestuffs headed
through Damascus: the first led from Baghdad to Damascus to Jerusalem
and Cairo, the other went to Damascus to Mosul to the Black Sea to
Byzantium (Istanbul).
Venice was one of the major early centers for imported dyestuffs,
supplying Brazilwood (Caesalpinia sappan) from the East, lac (another
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insect dye) and indigo from India from the fifteenth century CE onward.
Dyers of Italy soon became adept in their use; in 1429 the Venetian
dyer’s guild wrote a book for its members containing a number of
different dye recipes, including Brazilwood and lac. The Plictho de Larti
de Tentori by Venetian author Giovanni Ventur Rosetti (sp - also listed
as Giovanventura Rosetti) in the 1540s lists instructions for using both
lac and indigo, as well as 217 other recipes for dyeing cloth, linen, cotton
and silk with many varieties of dyestuffs. It would remain the best source
for dyeing instruction for the next 200 years.
From Venice the dyestuffs were traded by ship around the coast of
France to Flanders, Southampton and London; in the Mediterranean at
Florence, Pisa and Genoa; and northward on the continent to the
distribution centers of Basle and Frankfurt (Schetky, 6). Basle was a
noted center of trade for saffron, the expensive yellow obtained from
certain species of crocus. In later years crocus were grown in that area
directly, and the crop became such a vital part of the local economy that
they crocus was featured on the city’s coat of arms. Frankfurt housed
trade fairs from the twelfth to fourteenth centuries that dominated the
trade of many dyestuffs, but mainly that of locally grown woad, the only
blue dyestuff available to European dyers before the coming of indigo.
Many regions in Germany specialized in growing and processing the
woad through its complex fermentation process, and strict legislation was
placed on every aspect of the trade.
The government of Spain controlled the trade of cochineal, the red
dye from the bodies of the Cochineal bugs of Central America. In 1587
approximately 65 tons were shipped to Spain, and from there northward
throughout Europe. Italian dyers shunned cochineal in favor of the
already established dye kermes, made from the dried bodies of the
female shield louse or scale insect (Kermes ilicis) (Schetky, 4). It’s use
was first recorded in 1727 BCE and it was long the standard red dye for
silk, wool and leather, but the intense colorific value and relative
cheapness of cochineal soon eliminated most of the kermes use in
England, so Spain hung on to control of their lucrative monopoly.
European dyers reached their height of skill in the thirteenth
century, mainly due to the guild systems who vigilantly maintained a
high standard of quality. In many countries dyers were graded by the
guild system, the master dyers being allowed to use the major “fast” dyes
18
while their lesser colleagues were restricted to the slower, “fugitive”
dyes. In some places it was forbidden to possess, let alone use, major
dyestuffs unless you were a member of a guild. In Germany, the dyers
and woad workers were regulated by the guilds, each grower having to
present his crop to a “sworn dyer” to determine its quality, weight and
condition before it could be sold. (Grierson, 8-9) English producers of
woad had fewer restrictions, mainly that of a proclamation in 1587 to
restrict growers to certain field size and ensure that no woad mills were
sited within three miles of a royal residence, market town or city because
of the highly offensive odor they emit. Even the local doctors in Venice
in 1413 city fathers to prohibit dyeing with either woad or ox-blood after
March first because of the “unhealthy smell.” France had developed an
extensive and efficient textile industry by the 13th century and also
increased the dyers craft by developing varied techniques to achieve
additional colors from the basic dyestuffs. At the end of the 16th century,
there were over 220 master dyers listed in Paris alone.
While the powerful guild system had numerous dyestuffs with
which to blend their color palates of fiber for the bluebloods and wealthy
merchants, dyeing in the lower classes was a bit more restrictive.
Without the money (or connetions) to buy indigo, cochineal and
turmeric, clothing in the country tended to natural colors – whites,
blacks, browns, grays, and tans of the natural colors of the fibers
themselves, with the reds, greens and yellows of local plants used for
both food, medicine and dyes. In short, home dyers used any plants they
could lay their hands on that would give a good color. Some colors were
even derived accidentally. Washing beehives in preparation for making
mead could yield yellows and golds. Blackberries and Bilberries that
stained the fingers of pickers could also be used to achieve pale blues
and purples, although these were not often color or lightfast. In England,
the multitudinous variety of lichens and mosses produced greens, grays
and browns.
By the seventeenth century a worldwide shipping and trading
network was in place, allowing dyestuffs from all parts of the world to be
brought to Europe. Legislation from earlier centuries to protect the
growers and users of specific dyestuffs was overturned in favor of new
demands and standards set by the growing consumer-focused society
who wanted more colors and better quality. In the eighteenth and
19
nineteenth centuries the practice of colonialism insured that there would
always be a supply of foreign dyestuffs, and the Industrial Revolution
met the demands of large-scale productions while finding new ways to
make the colors brighter and longer-lasting to wear and washing.
As textile weaving technology advanced with the advent of
machines to spin, design and weave fabric, dyers were forced to be able
to produce dyes with exact shades, matching color lots and most
importantly, ones that would stand “fast” to the new mechanical and
chemical processing. In addition, exporters wanted colors that would
stand up to tropical sunlight and still be exotic enough for foreign tastes.
Dyers in turn demanded from their supplier’s purer chemicals and
dyestuffs of consistent quality. Hand in hand, dyers, manufacturers,
chemists, and dyestuff producers worked hand in hand to keep up with
the progress of technology. Chemists in many countries had found a
means of extracting highly concentrated powders or pastes from
traditional dyestuffs that made stronger colors, such as cochineal carmine
and madder garancine. Other procedures were used to extract indigo that
gave us sulphonated indigo and Saxon blue. A few novel dyes
(precursors of future chemical dyes) such as the yellow obtained from
picric acid also made an appearance. With the tremendous rise in the
interest of Chemistry in the mid nineteenth century, several important
innovations in dyeing came about. W.H. Perkin, a student of celebrated
European scientist Wilhelm von Hoffman, accidentally discovered the
first synthetic dye in an attempt to synthesize quinine. The 18-year old
student’s purple precipitate, later called mauviene, was quickly put into
industrial application, allowing the young Perkin to start his own factory
in London to commercially produce his dyestuff. Two years letter a
synthetic red dye called magenta or fuchsine was patented in France, and
hardly a year passed until the end of the century without a new synthetic
dye being patented.
Eventually, the old natural dyes lost popularity in favor of the
newer synthetic ones. By the end of the nineteenth century a few Scottish
tweed producers were the only ones still using natural dyes, and now the
use of natural dyes on a commercial scale barely exists, mainly in remote
areas where people have either little access to synthetic dyes or a vested
interest in retaining their ancient dyeing customs. Use of natural dyes is
gaining popularity again with the renaissance in hand crafting, most
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notably in the fields of spinning and weaving, basketry, papermaking and
leather craft. There is also renewed scientific and historic interest in
natural dyeing, both to help identify dyestuffs in recently discovered
archaeological finds and to preserve the dyed textiles housed in museums
and private collections.
As Su Grierson says in her book Dyeing and Dyestuffs, “Whilst
the dyeing industry of today keeps pace with modern science, the future
use of natural dyes will also follow a new path, but one firmly.

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