Acid dyes
Introduction
• Acid dye sare sodium salts of organic sulphonic acids
• Acid dyes are water soluble anionic dyes.
• Acid dyes are mainly used for dyeing Polyamide fibres (Wool, Silk &
Nylon)
• Ionic bond is formed to retain dye with fibre
• Acid dyes are classified based on chemical structure and method of
application.
Examples of Acid dyes
Sulphonic acid
Chromophores – Colour producing substance
Auxochrome – Increase the intensity of colour
Water soluble group – Sulphonic acid
Classification based on chemical structure
• Chemically, acid dyes are classified as:
• (i) Monoazo, e.g., Metanil Yellow and Acid Orange II; bisazo, e.g., Red
G and 2B,
• (ii) Nitro, e.g., Picric acid,
• (iii) Nitroso, e.g., Naphthol Green B,
• (iv) Triphenylmethane, e.g., Acid Magenta,
• (v) Xanthene, e.g., Rhodamine B, Acid Violet B,
• (vi) Azine etc
Classification based on application
• Class I: Strong or levelling or equalizing dyes, low affinity
• Class II: Milling dye, moderate affinity
• Class III: Super-milling dye, very high affinity
Table 1. Characteristics of various classes of acid dyes
• The structure of Silk can be represented as H2N–S–COOH.
• ‘S’ being the Silk fibre part with two different terminal groups, viz. –
COOH and –NH2 and few intermediate –CONH groups.
• The –NH2 group controls dyeing behaviour and is the dye site in
dyeing with anionic dyes.
Acid dyes on Silk
• Acid dyes possess lower affinity for silk as compared to that for wool
and lesser problem is encountered in level dyeing.
• Super milling dyes show very good fastness due to a long alkyl side
chain in the molecule.
Dyeing mechanism on silk
• Silk retains –NH2 and –COOH groups at terminal ends and is capable
of taking part in chemical reaction.
• Based on this, chemical structure of silk may be better represented as
H2N–S–COOH, where ‘S’ denotes rest part of Silk structure.
• When Silk is immersed in water, a proton (H+) – attached to the
carboxylic group at one end of Silk – is transferred to –NH2 group at
the other end of the fibre so that the two ends of Silk chain acquire
opposite electrical charges and the resulting ion is called zwitter ion:
• H2N–S–COOH → H3N+–S–COO-
• On addition of acid in bath containing wool with zwitter ions, some of the
negatively charged carboxylate ions (–COO−) take up proton released by
acid into solution and are transformed to electrically neutral carboxylic acid
groups (–COOH).
CH3COOH ↔ H+ + CH3COO-
H3N+–S–COO− + H+ CH3COO− ↔ H3N+–S–COOH
Dye SO3Na Dye-SO3- + Na+
Dye-SO3-Na+ + H3N+–S–COOH Dye-SO3-NH3+-S-COOH
• Rate of neutralisation of (–COO−) groups is proportional to the moles of
acid added in the bath.
• At the same time, the acid anions, released from acid are absorbed by the
positively charged amino ends of silk forming ionic bond.
Dyeing Recipe:
Acid dye x%
Acetic acid 2%
Na2SO4 10%
MLR 1:40
pH 4-5
Temperature 100°C
Time 1h
Dyeing procedure
• Exhaust dyeing at neutral or acidic pH is widely used method which starts
at 40–45°C followed by addition of acetic acid (2–4%) and Glauber’s salt
(5–10%) in bath to maintain a pH ~ 4–5.
• Dye is added and dyeing is continued for 10 min.
• Temperature is raised to 80–85°C in 45 min – dyeing at higher temperature
beyond this reduces lustre.
• Dyeing is continued for further 30–90 min to promote diffusion of dye into
fibre improving wash and rubbing fastness.
• A thorough wash removes superficial dyes. Strong acid dyes can also be
applied at pH ~ 3–4 using HCOOH (1–3%) and Glauber’s salt (5%).
Effect of Acid:
• Acid dyes are not taken up by protein fibre unless acid is added to bath.
• Acid provide exhaustion of acid dyes to the fibres
• Immersion of protein fibre in water transfers the terminal H atom from –
COOH and at another end the –NH2 group is protonated.
• During this process, carboxylic ion is formed at one end of fibre (COO−)
while amine ion (NH3+) at the other making the fibre oppositely charged
(zwitter ion).
• Addition of acid makes the fibre cationic in nature through attachment of H
atom of acid to the COO− ion making it COOH again.
Effect of Salt
• Salt act as retarding or levelling agent by controlling the dye uptake,
because acid dye have high affinity for polyamide fibres.
• If levelling agent is not added it will lead to unlevel dyeing.
• Salt occupies the dye sites (NH2) of silk temporarily. At higher
temperature, salt reacts more with water and dye sites remain free
for dyes to get attached to amino groups.
Effect of process parameters - Temperature
• Acid dyes are not transferred from bath to fibre below 39°C. Temperature
promote exhaustion.
• Efficient dyeing results are obtained if dyeing is started at about 40°C,
raised slowly to boil and dyeing is further carried out at boil for desired
time; slow rise in temperature causes replacement of CH3COO− ions at a
specific rate avoiding unlevelled dyeing.
• Beyond this temperature rate of adsorption increases and the trend varies
from one type of dye to other.
• Milling acid dyes have a minimum temperature of exhaustion at 60°C, but
at 70°C, transfer of dye is fast.
• Super-milling dyes cause level dyeing only at boil.
Fastness properties of Acid dyes on Silk
• Acid dyes produce brilliant shades with good light fastness on Silk.
• Poor to moderate wash fastness which can be improved by treatment
with cationic dye–fixing agent (2–4 g/l) at 40–50°C for 20 min.
• Acid dyes generally show poor coverage on silk necessitating topping
with basic dyes to produce levelled brilliant shades
End of the lecture
