Azo dyes

Azoic Colors
It is an ingrain dye and hence contains two components i.e.
Naphthol and Base.
Both of above are water soluble and combined to form azoic
pigment.
Azoic pigment is formed in fiber and thus washing fastness
is good.
It is sometimes formed on the surface and come out on
rubbing and hence possess poor rubbing fastness.
Azoic colors are also called Ice Colors and the reason is that
the base is converted by diazotisation, which requires very
cold conditions.

Naphthols and Bases

Naphthol is also known as azoic coupling component.
These are acylides are of BON (beta-oxy naphthoic acid).
Various types of naphthols can be Naphthol AS,
Naphthol ASBS, Naphthol ASBR etc.
Base is also known as the Diazotised base. This acts as a
coupling reactant along with the naphthol.
These are nomenclatured on the basis of color e.g. Fast
Red Base.
The purpose of diazotisation is to improve solubility.

Dyeing Process of Azoic Colors

The Dyeing process is carried out in three successive steps, which
are as follows:
Naphtholation
Naphthol is water insoluble. Thus the process of making insoluble
naphthol soluble is known as Naphtholation.

The sodium salt of naphthol obtained above is not very much stable
as CO2 reacts with it water to form carbonic acid and it converts it to
free naphthol form so we should avoid any type of acidic exposure.

The sodium salt is thus treated with HCHO.

When this methylol compound is exposed to high temperature then it gets converted to methylene
compound and naphthol loses its ability to react with diazotised base.
The naphthols are classified on the basis of substantivity i.e. low and high substantivity naphthols.

Diazotisation
This process involves conversion of the base in the soluble
form i.e. hydrochloride form which has better solubility.
R-NH2 + HCl
R-NH 3+Cl(Fast base)
(Hydrochloride base)
HCl + NaNO2
HNO2 + NaCl
R-NH+3Cl- + HNO2
R-N+=N + 2H2O

Cl(Diazotised base)
where R can be any aromatic group

..
At higher temperature, diazotized base formed becomes
highly unstable and hence backward reaction starts.
Hence the process is carried out at lower temp.
We add HCl which reacts with NaNO2 to form HNO2,
which helps in diazotisation and reacts with free base to
form hydrochloride form.
These can be slow coupling bases which require little
acidic conditions and fast coupling bases which require
stronger acidic conditions.

Coupling
The naphtholated fabric is passed through the diazotised
base solution for coupling reaction to take place.
This process of coupling is highly exothermic and hence
should be carried at low temp.
It also requires acidic conditions i.e. it requires 5-6 pH.
The CH3COOH besides maintaining the pH also acts as a
buffer to maintain the alkalinity of the solution constant.

Coupling Reaction

Some of the naphthol comes out of the fabric and reacts

with the diazotised base to give the azoic pigment which
reduces the washing fastness. Hence, strong soaping is
done to prevent the surface dye.
Moreover, azoic colors are not used as the process of
applying these dyes is very cumbersome.

Types of AZO dyes in accordance to

there nature
A. hazardous AZO-dyes
B. non-hazardous or safe AZO-dyes

Hazardous AZO-dyes

These dyes use AZO-groups as coloring agent,

upon cleavage these chemical groups release
amines, which are harmful,
they are used mostly for cotton dyeing,
cheapest alternative to reactive dyes ( best
industrial dye ),
good color fastness, dyeing process short and
easy,
pollute waste-water with heavy metals,
many AZO-dyes are subject to ISO 14000
legislation

B. non-hazardous or safe AZOdyes

Availability:
...of product:
1. not easy to purchase
2. not widely distributed
3. they are sold by weight and price is higher
then hazardous azo dyes
...of information:
1. information available in English, using
international standards

Some Examples

Ponceau 4R
Ponceau S, Acid Red 112
4-aminoazobenzene
4-amino-2',3-dimethylazobenzene

Advantages of azoic dyes

Available in bright shades mostly deep red,
yellow and orange.
Used for cellulosic fibres.
Vary from poor to excellent fastness to to light.
Fastness to washing, perspiration good to
excellent.
Disadvantages of azoic dyes
Heavy shades have poor fastness to crocking.