1 GENERAL INFORMATION 1.1 The sector
1.3 Some products
1.3.1 Organic dyes and pigments
[1, Hunger, 2003, 2, Onken, 1996, 6, Ullmann, 2001, 19, Booth, 1988, 20, Bamfield, 2001, 46, Ministerio de Medio Ambiente, 2003]
1.3.1.1 Overview
Dyes and pigments can be classified according to their chemical structure or their mode of application. The most important commercial products are the azo, anthraquinone, sulphur, indigoid, triphenylmethane and phthalocyanine dyes. Figure 1.4 shows the major chromophores and Table 1.1 shows the classification of dyes by use or method of application.
Figure 1.4: Major chromophores of commercially important dyes
Dyeing method Preferred substrate/
typical application Principal chemical class Solubility in water Reactive dyes Cotton
Azo, metallised azo, phthalocyanine,
anthraquinone Soluble Disperse dyes Polyester,
electronic photography Non-ionic Insoluble
Direct dyes Cotton, regenerated
cellulose Anionic, poly-azo Soluble
Vat dyes Cellulose fibres Anthraquinone, indigoids
Insoluble
Soluble leuco salts
Sulphur dyes Cotton Sulphur dyes Soluble
Cationic or basic
dyes Paper, polyacrylo nitril,
polyesters Triarylmethane Soluble
Acid dyes Nylon, wool, silk,
leather, paper, ink-jets Soluble
Solvent dyes Plastics, gasoline, oils,
waxes Azo, anthraquinone Insoluble
Table 1.1: Classification of dyes by use or method of application
N N
(a) Phthalocyanine dye (b) Triarylmethane dye (c) Indigoids (d) Azo dye
(e) Anthraquinone dye
Chapter 1
6 Dezember 2005 OFC_BREF Apart from one or two notable exceptions, all dye types used today were discovered in
the 1880s. The introduction of the synthetic fibres such as nylon, polyester and polyacrylonitrile during the period 1930 – 1950, produced the next significant challenge. The discovery of reactive dyes in 1954 and their commercial launch heralded a major breakthrough in the dyeing of cotton. Intensive research into reactive dyes followed over the next two decades and is still continuing today.
One important theme in research today is the replacement of tinctorially weak chromogens, such as anthraquinone, with tinctorially stronger chromogens, such as (heterocyclic) azo dyes.
Considerable activity is also being dedicated to high tech applications, especially in the electronics and non-impact printing industries.
1.3.1.2 Pigments
Pigments are defined as colouring agents that are practically insoluble in the application medium, whereas dyes are colouring agents that are soluble in the application medium.
In colouring, the crystalline pigment is applied in the solid state, not in the dissolved form, to the medium being coloured. Both the chemical and the physical properties of the pigments (e.g.
particulate size, particulate size distribution, special types of surface and specific surface area, crystal modification, and crystal form) are important for their industrial application.
Many organic pigments and dyes have the same basic chemical structure. The insolubility required in pigments can be obtained by excluding solubilising groups, by forming insoluble salts (lake formation) of carboxylic or sulphonic acids, by metal complex formation in compounds without solubilising groups, and particularly by incorporating groups that reduce solubility (e.g. amide groups).
Figure 1.5 shows the largest areas of use of organic pigments.
Printing inks 50 %
Paints and coatings
25 % Plastics
20 % Other
5 %
Figure 1.5: Main uses of organic pigments
The remaining organic pigments (“Other”) are used in textile printing and a number of smaller sectors, including contactless printing processes, office articles and accessories (e.g. coloured pencils, crayons, chalks), and the colouring of wood, cosmetics, and paper.
1.3.1.3 Economics
The scale and growth of the dyes industry is linked to that of the textile industry. World textile production has grown steadily to an estimated 35 million tonnes in 1990. The two most important textile fibres are cotton and polyester. Consequently, dye manufacturers tend to concentrate their efforts on producing dyes for these two fibres. The estimated world production of dyes and pigments in 1990 was 1 million tonnes. The rapid growth in the high tech uses of dyes, particularly in ink-jet printing, is beginning to make an impact. Although the volumes in this area remain small in comparison to dyes for traditional applications, the value will be significant because of the much higher price.
DyStar 25 %
Ciba 13 % Clariant
Yorkshire 8 % 5 % Japan
9 % Other Asia
40 %
Figure 1.6: Share of the world textile dye market attributable to major manufacturers [20, Bamfield, 2001]
North America 32 %
South America 4 % Africa and Middle East Asia Pacific 5 %
26 % Eastern Europe
3 % Western Europe
30 %
Figure 1.7: Share of the world organic pigments market attributable to main geographic regions [20, Bamfield, 2001]
The Western European share of world production has declined from 95 % in the early 1900s to about 40 %, taking into account that a large part of US manufacture and that of other countries is based on Western European subsidiaries. This decline is coupled with an increase of production in commodity dyestuffs in lower cost countries such as India, Taiwan and China.
The world output of organic dyes is estimated to be 750000 tonnes per year [6, Ullmann, 2001].
The major European dye manufacturers have undergone major reorganisations, mergers and acquisitions to focus on “core” activities (Table 1.2).
Chapter 1
8 Dezember 2005 OFC_BREF
Country Current Company Original companies
Germany Dystar Bayer, Hoechst, BASF, textile dyes from Zeneca Clariant Sandoz, Hoechst Speciality Chemicals
Switzerland
Ciba Speciality Chemicals Ciba-Geigy
UK Avecia ICI
Yorkshire Crompton and Knowles (US) Table 1.2: Restructuring of the major Western European dye manufacturers [20, Bamfield, 2001]
1.3.2 Active pharmaceutical ingredients (APIs)
[2, Onken, 1996, 6, Ullmann, 2001, 21, EFPIA, 2003, 35, CEFIC, 2003]
1.3.2.1 Overview
Active Pharmaceutical Ingredients (APIs) are based on organic molecules which have been synthesised and modified to provide medicinal products and comprise the largest segment of available drugs. Biotechnology is part of the pharmaceutical industry today, but drugs based on organic chemistry remain the largest part of R&D and comprise the largest percentage of new drugs launched yearly. Figure 1.8 gives some examples, but in reality the variety in the world is enormous.
(a) Benzodiazepams (b) Penicillins (c) Steroids (d) Indole alkaloids (e) Barbiturates (f) Sulphonamides (g) Pyrazolones
Figure 1.8: Examples of APIs
1.3.2.2 Legal requirements and process modifications
Where API manufacture on a site requires the observance of the rules of current Good Manufacturing Practice (cGMP) or approval by the European Medicine Evaluation Agency (EMEA), the United States Food and Drug Administration (FDA) or other applicable medicine approval authorities, process modifications can be only carried out fulfilling the required variation procedure. This represents a serious obstacle for the redesign of existing processes.
This is even more the case if the API is supplied to a number of different marketing application holders (which is the case for about 75 % of the total volume of API production).
1.3.2.3 Economics
The pharmaceutical industry is a major industrial asset to the European economy, strongly research-based and one of the best performing high technology sectors. Europe produces more than 40 % of the world’s pharmaceutical output by value, making it still the world’s leading manufacturing location ahead of the US (over 30 %) and Japan (20 %).
1985 1990 2000 2001