Protein Textile Dyes

What are protein textiles?

Proteins are composed of long chains of amino acids, which coil up on
themselves due to hydrogen bonding and other intramolecular forces. Most
protein textiles are derived from structural proteins produced by animals, in
particular wool and silk. Wool is largely composed of the same protein as
your nails and hair- keratin2.

Proteins contain two major functional groups which affect their ability to
interact with dyes: -NH2 which can be protonated to form a positively
charged group, and -COOH, which can be deprotonated to from a negatively
charged group. They are best dyed by acid dyes and mordant dyes.

Acid dyes
Acidic dyes are highly water soluble, and have better light fastness than
basic dyes. They contain sulphonic acid groups, which are usually present as
sodium sulphonate salts. These increase solubility in water, and give the dye
molecules a negative charge. In an acidic solution, the -NH2 functionalities of
the fibres are protonated to give a positive charge: -NH3+. This charge
interacts with the negative dye charge, allowing the formation of ionic
interactions. As well as this, Van-der-Waals bonds, dipolar bonds and
hydrogen bonds are formed between dye and fibre2.
As a group, acid dyes can be divided into two sub-groups: acid-leveling or
acid-milling2.

Acid-leveling dyes

These planar dyes tend to be small or medium sized, and show moderate
inter-molecular attractions for wool fibres. This means that the dye
molecules can move fairly easily through the fibres and achieve an even
colour2. This is somewhat similar to the process that occurs during
chromatography- the molecules with the strongest affinity for the substrate
move the least distance from the point of origin whereas molecules with less
affinity move much further. However, the low affinity means that these dyes
are not always very resistant to washing2`.

Acid-milling dyes
Acid-milling dyes are larger than acid-leveling dyes, and show a much
stronger affinity for wool fibres. Because of this, the resultant colour may be
less even (see explanation above), but they are much more resistant to
washing.
As well as intermolecular interactions, intramolecular interactions play an
important part in the properties of the dye. Compare the two molecules
shown below. They are isomers, but the one on the right (with hydrogen
bonding) shows a much greater resistance to washing in alkali, and much
increased light fastness2.

Acid dye colours

Usually, yellow, orange and red acid dyes are azo compounds, with blues and
greens often come from the carbonyl class, particularly anthraquinones (see
the example below)2.
An example of an acid dye is Alizarine Pure Blue B. It is a sulphonated
aminoanthraquinone, and can be manufactured in two ways1:
By condensation of 1-amino-2,4-dibromoanthraquinone with aniline, then
treatment under pressure with sodium sulphite in a phenol solvent1.

By condensation of sodium 1-amino-4-bromoanthraquinone-2-sulphonate

(bromamine acid) with aniline and a copper salt1.

Mordant dyes
Mordant is a Latin word meaning 'to bite'13. Mordants act as 'fixing agents' to
improve the colour fastness of some acid dyes, which have the ability to form
complexes with metal ions. Mordants are usually metal salts; alum
[KAl(SO4)2.H2O] was commonly used for ancient dyes, but there is a large
range of other metallic salt mordants available. Each one gives a different
colour with any particular dye, by forming an insoluble complex with the dye
molecules. Chromium salts such as sodium or potassium dichromate are
commonly used now for synthetic mordant dyes. The diagrams below show
C.I. Mordant Black 1 with and without a chromium (III) ion. Chromium (III)
forms 6-coordinate complexes, so two Mordant Black molecules would attach
to one ion. Only one is shown below for clarity.

Mordants do not have to be metal salts. Organic molecules such as tannic

acid and tartaric acid can be used as well.