Lec # 6

Textile Dyes & AZOIC

Dyeing
Dr. Rehan Abbasi COLORS
 INTRODUCTION
It is called azoic colour and not a dye as there is
no dye present. The dye is formed on the
substrate itself i.e. on fibre, yarn or fabric.

To have a azoic colour we require 2

components
• Naphthol (coupling component) and
• Base or salt (Diazo component)
 INTRODUCTION
• There are 34 naphthols and 50 bases/ salts
• The combinations can produce about 2000
shades but only a few of them are used as
 either they are very expensive and there are
cheaper substitutes for them, or
 they have poor reproducibility and
brightness
 HOW IS COLOUR FORMED?
NH2
OH

Β naphthol
P-nitroaniline

NO2
NH2 N NCl- N=N NO2

OH

OH

NO2 NO2 On coupling, colour is formed

Diazotised p-nitro aniline
 NAPHTHOLS
O O
H H

COOH
β naphthol BON acid (β oxy
napthoic acid)

β naphthol has no affinity so then the cloth has to be dried and

then coupled. This was a limiting factor as drying is a costly process
and during dyeing the naphthol even migrates
 NAPHTHOLS….CONTD
OH

CONH

Naphthol AS
Has affinity for cotton and so drying is not
required. It is a naphthol developed from BON
acid
 NAPHTHOLS….CONTD
Anilides of BON acid (RED naphthols)
OH OH

+ H 2N
COO
CONH
H

By changing amine, different naphthols can be

obtained.
NH NH
NH
CH3 NO2

Naphthol ASD Naphthol ASBS Naphthol AS-SW

 DIAZOTIZABLE BASES
NH 2
Aniline derivatives

R
Examples NH2 NH2 NH 2
NO2

NO2 Cl OCH 3

Red OrangeGC Bordeaux GP

A base will give only 1 colour but can have tonal changes
 DIAZOTIZABLE
BASES...CONTD
Colour Coupling component Diazo component

Yellow Amides of acetoacetic acid

(Ex - Naphthol ASG)
Anilides of Bon acid (Red Aniline derivative
Red
naphthol)
6-methoxy derivative of
Bon acid OR
Bordeaux

Red acid Aminoazo benzene derivative

Violet Red naphthol p-Benzoyl amino anilines

Green Green naphthol Violet/Blue BB base

Brown Anthracene derivative Various fast bases or salts

(Brown naphthol)
Red naphthol Black bases
Black
OR Black naphthol Red base or salt
APPLICATION OF AZO DYES

1. Treatment with naphthol

2. Diazotization of base
3. Coupling of naphthol
4. After treatment
 TREATMENT WITH
NAPHTHOLS
Naphthols are not soluble in water.

OH O-Na+
NaOH

CONH CONH

Dissolution can be done by 2 methods -

1. Hot dissolution method
2. Cold dissolution method
 HOT DISSOLUTION METHOD

•Naphthol is pasted with a wetting agent such as (sulphonated

castor oil) and a fine paste is prepared.
•Soft water is added and dispresion is heated to near boil. If hard
water is used it may result in precipitation of the naphthol or alkali
• If soft water is not available, a sequestering agent is added
• Then calculated amount NaOH is added with stirring
• Naphthol dissolves slowly to give olive green to light brown
colour
• Solution is then cooled and diluted to required amount
 COLD DISSOLUTION METHOD

•Paste is prepared with wetting agent & NaOH & then

alcohol (ethyl alcohol) (1.5-2 times quantity of naphthol)
added
•Then cold water is added to get required concentration of
naphthol
•Generally used in printing where small quantity of liquor is
required to be used
 SUBSTANTIVITY OF
NAPHTHOLATE ION
•For exhaust/ batch method high substantive naphthol should

be used
•For continuous method, low substantive naphthol should be
used
•Direct dyes are negatively charged, and salt is added for its
exhaustion. Naphtols are also negatively charged and hence in
exhaustion method salt is added
•Within very short of time only a small amount of
naphthol is absorbed
 SUBSTANTIVITY OF
NAPHTHOLATE ION

Naphthols AS-D, AS, AS-OL have low substantivity

Naphthols AS-BR, AS-LC, AS-L3G have high substantivity
 DIAZOTIZATION OF BASE
+
O2N NH 2 + HCl O2N N Cl

H
H H
NaNO2 + HCl → HNO2 + NaCl

+ HNO 2
O2N N Cl
O2N N - N =OCl
-
+
H
H H H H

-
O2N N_+ _ Cl +
O2N N=N-OHCl -

H
 DIAZOTIZATION OF
BASE
•Diazotization reaction is carried out at 5-10oC which is obtained
by adding ice. Hence these colours are also called as ice colours
•To diazotise 1 mole of amine, 2 moles of hydrochloric acid and 1
mole of sodium nitrite is required
•In practice, amount of hydrochloric acid added is more than 2
moles
 DIAZOTIZATION OF
BASE
1. Base is pasted with wetting agent HCl is added and solution
is heated so that base dissolves
2. Water and ice added to bring down the temperature to 5-
10oC
3. In separate vessel, NaNO2 is dissolved and added to base
solution gradually with stirring
4. Presence of nitrous acid is checked with starch iodide
paper
5. Presence of HCl checked with congo red paper
6. Excess HCl is neutralized by adding sodium acetate which
reacts with HCl forming acetic acid and sodium acetate mixture
which acts as buffer of pH 4-5

Cloth is run in naphthol for half an hour, squeezed and then

After naphtolation and coupling, the fabric is washed
with water and then soaping treatment is given.
Soaping improves the wash fastness as well as the
light fastness.
 ALTERNATIVE OPTIONS
Since the whole naphtolation, diazotization and coupling is a
lengthy process, the following different systems were developed –
1.Fast Colour salts – Stabilised diazotised bases
Cl

+ Fast Red Salt RC

N _ N ZnCl-2-

OCH3
2

All are formed by dyeing diazotised base under vacuum and then
treating with required chemical which results in stabilised salt.
Most common chemical is zinc chloride
 ADVANTAGES OF AZOIC COLOURS

• Does not have any solubilising group so have

good wash fastness. The colour is
mechanically entrapped and so cannot be
removed easily
• Bright shades produces
• Cheap to apply
• In deep shades, light fastness is also good
• Choice of application of colours is taken
advantage off in printing – batik, tie and dye
etc.
 DISADVANTAGES OF AZOIC COLOURS

• Colour range/ gamut is limited – only orange,

red, yellow, blue, brown & blacks can be
produced
• Poor rubbing fastness
THANK YOU