Azoic Color
The dyes which contain insoluble azo group (-N=N-) are known as azoic dyes. These dyes are not found in
readymade form. They are produced through a process which creates the colored material directly on the
fabric by a reaction between two compounds namely, di-azo compound or diazole base and coupling
compound i.e. Naphthol. Azoic dye is one type of ingrain dye i.e. it is produced during dyeing process inside
the fiber. The formation of an insoluble azoic pigment was first patented by Thomas and Robert Holliday in
1880.
Different Names of Azoic Dyes:
Naphthol Color:
To make the fabric colored the fabric is first impregnated with aryl amide or sodium salt of -naphthol to
make substantive towards cellulose. As the first coupling compound is naphthol, it is called naphthol color.
Ice Color:
For the diazotization reaction very low temperature is required (0 0-50C) which is normally created by ice water.
So, it is called ice color.
Pigment Color:
Here two components which react together to form azoic color, i.e. a base and naphthol are both soluble in
water, but the resultant color are insoluble in water. That is to say azoic color containing azo group, is
insoluble in water. So it is called azoic pigment.
Magic Color:
Azoic colors are called magic color due to their versatility. Different colors are obtained by combining different
bases with same naphthol within very short time. Again different colors can also be obtained by combining
different naphthol with same base. So, they are called magic color.
Fast Color:
As the azoic colors are insoluble in water, they have good wash fastness. So, azoic colors are called fast color.
Developed Color:
As the dye is formed inside the fiber during dyeing process by chemical reaction it is called developed
dye/color.
Properties of Azoic Color:
Cellulose specially cotton, flax (linen), rayon, jute, hemp, and silk, nylon, polyester, acetate fibers are
dyed and printed with azoic dyes.
Color is formed from water soluble components but produced color is water insoluble.
Azoic colors have excellent light fastness with rating 6-7.
Azoic dyed and printed materials have very good wash fastness as it is insoluble in water. The rating is
4-5.
Azoic dyes are characterized by their very bright red and orange colors. Though various shades can be
produced by them.
Azoic dyed and printed materials have poor rub-fastness. This occurs due to the formation of insoluble
azoic dye on fiber or fabric surface which is not removed during final stage of dyeing or printing.
In case of viscose and cotton azoic dyes may cause delustured effect named blinding effect.
Prepared by Sumon Mazumder
Assistant Professor, Department of TE
Chemistry of Dyeing with azoic Dye:
Naphtholation:
Naphthols are insoluble in water and they are converted into water soluble compound by treating with alkali.
OH ONa
+ NaOH + H2O
-naphthol (Insoluble) Alkali Soluble Na-Salt of -naphthol
This salt solution is used for the impregnation of fabric.
Diazotization:
A base containing amino group (-NH 2) reacts with the NaNO2 (Sodium Nitrite) to form a solution of diazonium
chloride of that base in presence of excess HCl at 0 0-50C temperature.
NH2 NH3+Cl-
+ HCl
Aniline (Base)
NaNO2 + HCl HNO2 + NaCl
NH3+Cl- 00-50C N=N-Cl
+ HNO2 + 2H2O
Nitrous Acid
Benzene Diazonium
Chloride
Coupling/Developing:
The impregnated material is treated in a bath containing diazonium solution to carry out to coupling and thus
color is produced inside the fabric. The pH maintaining is important.
Coupling OH
ONa N=N-Cl N=N
+ + NaCl
Na--Naptholate Benzene Diazonium Salt Insoluble Azo Group
Chemicals Used for Naphtholation:
1. Naphthol:
Naphthol is the coupling component, which reacts with di-azo components and this azoic color is formed.
2. Alkali:
Naphthol is not easily soluble in water. So alkali is used to convert naphthol to soluble Na-Naptholate. Thus
alkali makes naphthol substantive to cotton fiber.
OH ONa
+ NaOH
CONH CONH
Caustic Soda
Naphthol–AS [Insoluble] [Alkali] Na–Naptholate [Salt] (Soluble)
Prepared by Sumon Mazumder
Assistant Professor, Department of TE
OH ONa
+ NaOH
–Naphthol Alkali Na––Naptholate
3. Common Salt:
Common salt (NaCl) is used as an electrolyte to increase substantivity of naphthol to fiber.
4. Formaldehydes:
In the bath, Sodium Naptholate shows the tendency to be converted to free naphthol by oxidation process.
Formaldehyde prevents that tendency. But, formaldehyde is not used for all time. Only in the cases where
naphthol solution has to keep for long time formaldehyde is used.
Problems in Dyeing with Azoic Dyes:
1. Uneven Shade:
The reasons for uneven shade are:-
a) Faulty liquor movement
b) Faulty fabric movement during naphtholation
c) Improper naphtholation
d) Improper Hydro extraction
2. Naphthol Migration:
The naphthol in fabric goes to base solution of the bath and reacts with base other than in the fabric. This is
called naphthol migration. This occurs due to:-
a) Improper selection of naphthol
b) More moisture in fabric.
3. Slow Coupling Reaction:
The reasons for slow coupling reactions are:-
a) Improper selection of base to mix with naphthol
b) Wrong range of pH in bath i.e. more acidity.
4. Affinity of Base towards Cellulose:
Azoic base should have affinity towards naphthol. But sometimes it shows affinity towards cellulose. This
hampers dyeing.
5. Blinding Effect:
In case of rayon dyeing a blinding effect may occur due to–
a) Presence of excess alkali during naphtholation.
b) Improper value of pH
c) Presence of alkaline group in coupling bath.
This blinding effect may be prevented by using alkali blinding agent (e.g. alum)
6. Pigment on Fiber Surface:
The reasons for this are:-
a) Unfixed dye on fiber surface (Unreacted naphthol)
b) Improper washing after dyeing.
This can be prevented by–
a) Using blinding agent for alkali
b) Curing process.
7. Naphthol Decomposition:
Prepared by Sumon Mazumder
Assistant Professor, Department of TE
Atmospheric CO2 may decompose naphthol. It can be prevented by using salt solution with naphthol.
Stripping of Azoic Dye:
The removal of dye from dyed material is called stripping. Stripping at azoic dye is carried out due to following
reasons:-
a) For uniform shade.
b) For faulty dyeing.
Stripping of azoic dyes is done in reduction process. By reduction the azo group is converted to two colorless
amino groups which go out from fabric is washed.
[H]
–N=N– –NH2 + –NH2
Azo Group Amino Group
Difference between Azo dyes & Azoic Dyes:
Azo Dyes Azoic Dyes
1. Contain soluble azo group 1. Contain insoluble azo group
2. Readymade dyes 2. Not readymade dyes
3. Don’t require diazotization and coupling reaction 3. Require diazotization & coupling reaction
4. Don’t produce so bright shade 4. Produce bright shade
5. Don’t have good wash fastness 5. Wash fastness is good
6. Simple dyeing and printing 6. complicated dyeing and printing process
7. Less costly 7. More costly
8. No ice is used 8. Ice is used
9. One bath process 9. Two bath process.
Prepared by Sumon Mazumder
Assistant Professor, Department of TE