What is a Dye/Dyestuff?

A dye is a coloured chemical synthesized from benzenoid hydrocarbons. These are derivatives of benzene compounds which have either coal tar or petroleum as a source material. Their uses range from food to fabrics to cosmetics.

There are two types of dyes, natural (animal or vegetable) and synthetic. Alhtough nowadays very few natural dyes are used by commercial enterprises.

A Revised Timeline:

In this section I will give you a timeline highlighting some important moments in the industry. (Please note this is a modified timeline from Susan C. Druding's Seminar in Seattle, 1982.
  • 2600 BC Earliest written record of the use of dyestuffs in China
  • 715 BC Wool dyeing established as craft in Rome
  • 327 BC Alexander the Great mentions "beautiful printed cottons" in India
  • 236 BC An Egyptian papyrus mentions dyers as "stinking of fish, with tired eyes and hands working unceasingly
  • 2ND and 3RD Centuries AD Roman graves found with madder and indigo dyed textiles, replacing the old Imperial Purple (purpura)
  • 3rd Century papyrus found in a grave contains the oldest dye recipe known, for imitation purple - called Stockholm Papyrus. It is a Greek work.
  • 273 AD Emperor Aurelian refused to let his wife buy a purpura-dyed silk garment. It cost its weight in gold. (Origins of Haute Couture? ;-) )
  • 400 AD Murex (the mollusk from which purpura comes) becoming scarce due to huge demand and over harvesting for Romans. One pound of cloth dyed with Murex worth $20,000 in terms of our money today (Emperor Augustus source)
  • 700's a Chinese manuscript mentions dyeing with wax resist technique (batik)
  • 925 the Wool Dyers' Guilds first initiated in Germany
  • 1188 the first mention of Guilds for Dyers in London
  • 1200's Rucellia, of Florence, rediscovered the ancient art of making purple dye from lichens sent from Asia Minor (similar to Orchils?)
  • 1321 Brazilwood was first mentioned as a dye, source from East Indies and India. (the country of Brazil was named for the wood found there, not vice versa)
  • Early 15th Century Cennino Cennini of Padua, Italy described the printing of cloth (block printing) in his treatise called Method of Painting Cloths by Means of Moulds.
  • 1429 the 1st European book on dyeing Mariegola Dell'Arte de Tentori was published in Italy
  • 1472 Edward IV incorporated the Dyers' Company of London
  • 1507 France, Holland and Germany begin the cultivation of dye plants as an industry
  • 1614 dyeing cloth "in the wood" was introduced in England: logwood, fustic, etc.
  • 1630 Drebbel, a Dutch chemist, produced a new brilliant red dye from cochineal and tin. It was used at Goblein (Paris) and the Bow Dyeworks (England)
  • 1689 the first calico printworks was begun in Germany at Augsburg and was later to grow into a large industry
  • 18th Century English dyehouse gets contract to dye the Buckingham Palace Guards coats with cochineal. This contract continued into the 20th Century still using cochineal.
  • 1766 Dr. Cuthbert Gordon patents Cudbear (derived from his mother's name) Cuthbert was prepared from a variety of lichens. Only one of 2 natural dyes ever credited to an individual (other is quercitron to Bancroft)
  • 1774 Swedish chemist, Scheele, discovered chlorine destroyed vegetable colors by observing a cork in a bottle of hydrochloric acid
  • 1774 Prussian Blue and Sulphuric acid available commercially. Prussian blue formed from prussite of potash and iron salt (copperas). Actually one of the early chemical dyes.
  • 1775 Bancroft introduced the use of quercitron bark as a natural dye. One of only 2 natural dyes whose discoverer is known, it yields a yellow, brighter than fustic, and is from the inner bark of No. American oak.
  • 1786 Bertholet, France, recommended chlorine water for commercial bleaching. Other oxidizing agents began to be used, too: hydrogen peroxide, sodium peroxide and sodium perborate.
  • 1785 Bell, England, who had invented printing from plates, developed roller printing
  • 1788 Picric acid available (yellow dye and disinfectant) could be dyed from acid dyebath on wool
  • 1790 Acid discharge of mordant printing developed
  • 1796 Tennant developed bleaching process
  • 1797 Bancroft develops a process for steam fixation of prints
  • 1823 Mercer discovered chromate discharge of indigo
  • 1834 Runge, a German chemist, noticed that upon distilling coal tar, aniline would give a bright blue color if treated with bleaching powder. This helped to pave the way to the development of aniline (basic) dyes 22 years later.
  • 1844 John Mercer discovered that treating cotton with caustic soda (lye) while under tension improved its strength, luster, dyeability, absorbency. The process was called "mercerization".
  • 1856 William Henry Perkin discovered the first synthetic dye stuff "Mauve" (aniline, a basic dye) while searching for a cure for malaria and a new industry was begun. It was a brilliant fuchsia type color, but faded easily so our idea of the color mauve is not what the appearance of the original color was.
  • 1858 Griess discovered diazotisation and coupling on/in the fiber
  • 1858-59 Magenta (fuchsin) discovered by Verguin the 2nd basic dye and more widely used than Mauve
  • 1861 Methyl violet, basic dye, by Lauth
  • 1862 Hofmann's Violet, Hofmann was one of the great dye chemists of all time
  • 1862 Bismarck Brown developed by Martius and Lightfoot, first soluble azo dye
  • 1863 Aniline Black, developed by Lightfoot, a black produced by oxidation of aniline on the cotton fiber.
  • 1866 Methyl Violet, basic dye
  • 1868 Graebe and Liebermann, German chemists, produced alizarin (synthetic madder). this was the first time a synthetic substitute for a vegetable dye had been manufactured. W.H.Perkin also synthesized it about the same time, but independently.
  • 1872 Methyl Green by Lauth and Baubigny, still in use, basic dye
  • 1873 Cachou de Laval, 1st sulphur dye, a brown, by Groissant and Bretonniere, France
  • 1875-76 Caro and Witt prepared Chrysoidine, 1st important member of azo class of dye
  • 1876 Caro, an important dye chemist, discovered Methyl Blue, an important
  • 1877 Malachite Green, basic dye by Dobner and Fisher
  • 1878 Biebrich Scarlet invented, a very pure red acid dye, rivalling cochineal in brightness
  • 1878 von Baeyer synthesized synthetic indigo. It was not marketed until 1897
  • 1880 Thomas and Holliday, England, synthesized the first azo dye formed on the fabric by coupling. Vacanceine red formed by treating fabric with napthol and then dipping in a diazolized amine, a very fast category of dyes.
  • 1884 Congo Red by Bottiger, first of the direct cotton dyes
  • 1885 Benzopurpurine, early direct dye by Duisberg, bright and highly substantive
  • 1885 Para Red dye brought out by von Gallois and Ullrich. (B napthol and nitraniline)
  • 1887 First azo mordant dye, Alizarin Yellow GG
  • 1887 Rhodamine B (brilliant red-violet) basic dye
  • 1890 Direct Black BH, first direct black
  • 1891 Diamine Green B, first green azo dye
  • 1891 Chardonnet built his first commercial plant at Besancon for manufacturing rayon, by the Chardonnet process.
  • 1891 Direct dye-Sky Blue FF, important blue for many years, good light fastness
  • 1893 2nd Sulphur dye, Vidal Black
  • 1895 Viscose method of making rayon invented by Cross and Bevan, England was begun. This is now the most common process for manufacture of rayon.
  • 1898 Direct Black E, a black dye of major importance
  • 1901 Rene Bohn patented his invention of Indanthrene Blue RS, the first anthraquinone vat dye, a category of dyes with extremely good fastness to light and washing
  • 1901 Bohn developed 2nd vat dye, Flanthrene a yellow
  • 1905 Thio-indigo Red, by Freidlander, 1st indigoid dye
  • 1908 Hydron Blue, a rival to indigo, developed by Cassella
  • 1915 Neolan dye, 1st metallized chrome dye, dyed from strong acid bath
  • 1921 Bader developed soluble vat colors, the Indigosols.
  • 1924 Indigosol 0, by Baeyer and Sunder, 1st commercial indigosol dye
  • 1951 Irgalan dyes introduced by Geigy, 1st neutral pre-metallized dyes (did not require a lot of acid as Neolans did) Cibalans are the same type.
  • 1953 Cibalan Brilliant Yellow 3GL, a dye which lead the way to discovery of the fiber reactive dyes was introduced
  • 1956 ICI in England introduced Procion, first range of fiber reactive dye - this dye was to have a major impact on industry as well as textile artists around the world.
  • 1957 CIBA introduces Cibacrons, a new range of reactive dyes and the first to compete with ICI's Procion series

A New Industry: Synthetic Dyes:

Until the mid 19th century, dyes were a very difficult thing to handle. Most dyes originated from vegetables. Sources and processes were still long and scarce.

The beginning of the synthetic dyestuffs industry began with William H. Perkin in 1856. His discovery of Mauveine (a purple dye) was the beginning of the synthetic over natural dye takeover. Perkin set up his industry in 1857, producing first just Mauveine and then other dyes.

A lot of research was launched in order to determine structures of natural colorants and then provide a synthesis route to them. This would mean ridding the process of extraction and also getting out of raw material problems. Imagine not need a field of plants to dye a shirt but a simple beaker and the right chemicals!

Alizarin was discovered in 1868, its source was from coal tar anthracene. Indigo, was only economically produced 20 years after its discovery in 1880. So although most dyes could be discovered, providing a simple route to these dyes was not always easy.

Sources for these dyes included aromatic compounds such as napthalene, anthracene and others. This is where Henry E. Armstrong's and William P. Wynne's work came in. Their work in deriving the patterns to substitutions of napthalene, was incredibly important. If you can predict what is going to happen in a reaction then you can devise a synthetic route to a specific product.

From then on it was just a case of experimenting with different substitutions and getting new compounds. The colours are only limited by the creativity of the synthesist, as you can clearly see there are now a huge array of colours available to the dye industry.

Manufacturing Processes Through Time:

Before the 19th century synthetic dye revolution, making dyes and pigments was a painstakingly long process. You had to extract the pigment and use large iron containers with wooden vats. Almost like boiling ingredients to get a coloured liquid. Imagine taking grass and heating it up with water to extract the chlorophyll and get a green colour. Unfortunately, once you do that you hope that the colour will last long enough. For your shirt you will need a lot of grass and it will take you time.

Since the discovery of Mauveine, there are now a varied set of tools available for dye manufacturing. These include things from better reaction vessels to vacuum pumps. Not only the better technologies involved in the processes, such as centrifugeing, coating of steel to prevent wooden vats soaking up the dyes, better linking between vessels to speed up manufacturing times. Other things to consider include the temperatures, concentrations of chemicals and pressures in each process. Unlike the 19th century, you can do this all automatically. Just imagine how hard it was back in the days before they even understood synthetic dyes!

Essentially, the dye industry from 2700BC until today has expanded from being a luxury for the few to a billion dollar industry which caters for everyone. Whether it be your clothes, where you live, your food, anything that has colour is due to the discovery of the humble pigment nearly 5000 years ago!