Abstract:

Acid Dyes are the dye of choice for solid color dyeing of silks,
wools, alpaca, mohair and other protein fibers, as well
as Nylon. Some folks even use them on leather, but test!
Excellent prices, bulk pricing, handy 2oz size. 52 beautiful,
vibrant, and some very hard to get colors! Can be painted on
as well. A process for dyeing nylon with acid or premetallized
acid dyes is provided wherein the dye bath is brought to a
temperature of 160 addition of sulfuric acid to lower the pH to
3.75-2.25, thereby improving dye exhaustion.

Introduction:
Acid dyes are highly water soluble, and have better light
fastness than basic dyes. The textile acid dyes are effective
for protein fibers such as silk, wool, nylon and modified
acrylics. 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 fibers are
prorogated 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 fiber. As a group, acid dyes can be divided into two sub-
groups: acid-leveling or acid-milling.

Chemical structure of acid dyes

These dyes are normally very complex in structure but have
large aromatic molecules, having a sulphonyl or amino group
which makes them soluble in water. Most of the acid dyes
belongs to following three main structural molecules,

1. Anthraquinon type
2. Azo dye type
3. Triphenylmethane type.

Different types of acid dye

The basic dyes are classified into several groups, based on the
leveling properties, economy of the dyeing and fastness
properties, however generally these are classified into these
three classes,

1. Neutral acid dyes:

These are supra milling or fast acid dyes, having medium to
good wet fastness properties, some of the dyes have poor light
fastness in pale shades. many of the dyes are used as self-
shades only. These are applied to the fiber in a weakly acid or
neutral pH.

2. Weak acid dyes

These dyes belongs to the milling class of dyes. These dyes
have good fastness properties but light fastness is moderate to
poor.

3. Strong acid dyes

These dyes are applied in a strongly acidic medium and also
called leveling dyes, however there wet fastness properties is a
limitation. These dyes are very good to produce the
combination shades.

Classification according to dyeing characteristics

Acid dyes are commonly classified according to their dyeing
behavior, especially in relation to the dyeing pH, their
migration ability during dyeing and their washing fastness.
The molecular weight and the degree of sulphonation of the
dye molecule determine these dyeing characteristics. The
original classification of this type, based on their behavior in
wool dyeing, is as follows:

1. Level dyeing or equalizing acid dyes;

2. Fast acid dyes;
3. Milling acid dyes;
4. Super-milling acid dyes.

Milling is the process in which a woollen material is treated, in

weakly alkaline solution, with considerable mechanical action
to promote felting. Dyes of good fastness to milling are
essential to avoid color bleeding during the process.

Properties of acid dyes

The main properties of acid dyes are,
Since these are sold as a sodium salt, therefore these form a
large anion in the aqueous medium.

1. These dyes are anionic in nature.

2. These dyes are suitable for wool, silk, polyamide and
modified acrylics.
3. These are applied from a strongly acidic to neutral pH bath.
4. These dyes have no affinity for cotton cellulose’s, hence not
suitable for cellulosic’s.
5. These dyes combine with the fiber by hydrogen bonds,
Vander Waals forces or through ionic linkages.

Mechanism of dyeing with acid dyes

Dissolution of dyes in aqueous solvent, produces a colored
anion,

The protein and polyamide fibers produce cationic sites in

water under acidic conditions, as the acidity of the solution is
increased more cationic sites are produced under these
strongly acidic conditions. These cationic sites are thus
available for the acid dye anions to combine with through
hydrogen bonding, vander waals forces or ionic bonding.
These linkages are strong enough to break, and thus dyeing
produced are fast.

Reaction between an acid dye and wool can be represented by

following equation:
A dyeing cycle for nylon filament dyeing

Fastness Properties of Acid Dyes

The wet and light fastness properties of the acid dyes vary
from poor to excellent, depending upon the molecular
structure of the dyes.

The fastness properties as per the category are as follows:

Neutral acid dyes:-
Since these dyes have very good leveling and migration
properties ,and have a low affinity for the fiber, therefore the
wet fastness properties of this class are generally poor.

Weak acid dyes or half milling dyes:-

These dyes have a medium to good affinity for the fiber and
are generally applied in a weakly acidic bath, shows medium to
good wet fastness properties. Strong acid dyes or super milling
dyes: These dyes have poor exhaustion properties, therefore
applied under very strong acidic condition, exhibit good
fastness properties.
Dyeing of nylon, polyester with modifications
The production of multi-colour effects has been done by the
help of differential-dyeing systems. The term “differential-
dyeing” is applied to fibers which are of the same basic type,
e.g., nylon but with different dyeing properties. To vary the
dyeing properties of the fiber (nylon), chemical modifications
are employed. In one case the substantivity of the fiber for
anionic dyes is modified by altering the amine end-group
content. This can be done by using a stabilizer during
polymerisation which has one or two carboxyl groups that can
react with the amino end groups of nylon polymer. The
stabilizer also has one or two sulphonate groups which make
the polymer anionic. An example of such a stabiliser is
disodium 3,5- disulphobenzoic acid – C6H3 (SO3Na)2 COOH, ie,
Na2DSBA. The reaction of the nylon polymer with Na2 DSBA is
as follows:

HOOC – Nylon Polymer – NH2 + HOOC – C6H3 (SO3Na)2 ––>

HOOC – Nylon Polymer – NHCO – C6H3(SO3Na)2 + H2O
(Cationic dye dyeable nylon)

Other alkali metal salts, e.g., lithium salt can also be used. 5-
sodium sulpho-isophthalic acid is also used to introduce
sulphonate groups in nylon 6 polymer. The introduction of the
sulphonate group increases the affinity for basic dyes while the
affinity for acid dyes is very low. In another modification, the
amine end-group content is varied which gives a differential
dye pick-up of acid dyes on nylon making it regular, light-
dyeable and deep-dyeable. The amine end – group content has
a predominant effect on dye pick-up when dyed with acid dyes.
The amino end – groups are the functional sites in nylon for
the adsorption of anionic dyes in acidic solution; the polymer
and acid dyes are ironically bonded in the acidic dye bath. By
introducing anionic sulphonate group (SO3–), nylon polymer
becomes cationic dye able. The reaction with basic dyes is as
follow:
Nylon polymer – SO3Na
Nylon polymer – SO3–+ Na+
Cationic dye – N+ + Cl–
Nylon polymer – SO3+
Cationic dye – N+
Nylon polymer – SO3—N+ — Cationic dye (Nylon dyed with
cationic dye).

In the second case, the nylon fiber is modified during

manufacture by introducing anionic sulphonate groups in the
nylon molecules. Such modified nylons have no substantivity
for acid dyes, but can be dyed with basic dyes. They are called
basic dyeable or cationic dyeable nylon.

As expected, the dyed shades obtained with basic dyes on

cationic dyeable nylon are bright. The bright shades coupled
with the luster of the fabric result in a silk-like appearance of
the fabric. However, when the dyed shades are further
subjected to any wet treatments, there is loss of colour. The
dyed shades are also unstable to high temperatures. Cationic
dyeable nylon printed with basic dyes when subjected to high
temperatures in the steam ager for fixation (~ 180°C), loses
colour. Keeping in mind the brilliancy of the shades and the
feel of the fabric, this system of basic dyes on cationic dyeable
nylon can be developed to produce silk-like fabrics. Besides
the appearance of the fabric, it is also economical to
manufacture. The main two problems to be addressed are
improving the wet fastness of the dyes and their high
temperature stability. Since this problem was faced by some
industrial units, a detailed study of the properties and dyeing
of cationic dyeable nylon was carried out.

Experimental
Cationic dyeable nylon fabric was not available in the local
market so the yarn was procured. Messrs Modipon kindly
supplied about 8 kg of cationic dyeable nylon yarn. The yarn
which was in the form of 4 cheeses of 2 kg each was wrapped
in polyethylene sheets and kept in the laboratory.
To study the properties of two different types of cationic
dyeable yarns, cationic dyeable polyester fabric was also
procured. Besides this, to study the physical properties of
polyamides, nylon 6 and nylon 66 fabrics (10 m each) were
procured. Cationic dyeable polyester, nylon 6 and nylon
66 fabrics were obtained in the pre-treated form, i.e., scoured,
bleached and OBA treated.

End-group analysis – Amine and carboxylic end groups of

nylons

The amino (–NH2) and carboxylic (–COOH) end groups of

cationic dyeable nylon, nylon 6 and nylon 66 were analyzed.

Dyeing of Cationic Dyeable Nylon (CDN) and Cationic Dyeable

Polyester (CDP) fabrics

Dyeing of CDN
The scoured/bleached and heat set fabrics were dyed with
basic dyes. The basic dyes were selected so as to cover the
entire gamut of shades. The seven basic dyes used for dyeing
and their concentrations are as given below:

 Coracryl Yellow C7G (200%).

 Coracryl Golden Yellow CGL (200%) – CI Basic Yel.28.
 Coracryl Pink CFG (200%) Basic Red 14.
 Coracryl Red C2B (200%) Basic Violet 16.
 Coracryl Blue C2R (200%) Basic Blue 54.
 Basicol Violet C3R.
 Basicol Brilliant Blue CBR (200%).

Concentrations (%): 0.1, 0.25, 0.5, 0.75, 1.0, 2.0, 4.0.

Dyeing was carried out in an HT/HP beaker dyeing machine at

pH 7. The dyeing liquor was prepared with 2 g/l disodium
hydrogen phthalate and 2 g/l sodium dihydrogen phthalate in
distilled water. The material to liquor ratio was kept at 1:50. 1
ml of 1% solution of cationic retarder was added to the dye
bath. The temperature cycle was:
After dyeing, the dyed samples were washed with 1 g/L non –
ionic detergent at 60 – 70°C. Addition of soda ash (sodium
carbonate) leads to loss of colour in some basic dyes. The dyed
samples were ironed. All the samples of cationic dyeable nylon
were dyed by the above method.

Fig: Dyes and

dyeing

Dyeing of CDP
The scoured, bleached and heat-set cationic dyeable polyester
(CDP) fabric was dyed with the above-mentioned basic dyes at
identical concentrations. Dyeing was carried out in an HT/HP
beaker dyeing machine under the following conditions:
 M: L Ratio 1:50
 2 g/L Sodium acetate
 3 g/L Sodium sulphate
 0.1 g/L Retarding agent

After dyeing, the dyed samples were rinsed and washed with 2
g/L non – ionic detergent at 60°C – 70°C. The dyed samples
were then subjected to mild ironing and stored in the dark.

The reflectance values of all the dyed samples of both cationic

dyeable nylon and cationic dyeable polyester were measured
on a Color Eye 7000A spectrophotometer (Gretag Macbeth
Computer Colour Matching System).

Discussion
A number of chemical treatments are available for improving
the wet fastness properties of dyes on textile fibers. These
treatment methods may involve increasing the molecular
weight of the dye so that it is rendered less soluble and
thereby improving the wet fastness. Alternatively, the after-
treatment agent may form a layer on the fabric which prevents
diffusion of the dye out of the fabric on washing. The nature of
the after treatment varies with the dyes used for dyeing and
the nature of the substrate. The interaction of the after-
treatment agent with the dye/substrate may be a chemical
reaction or by mere ion-ion interactions.