TEX 3101, WPT-II NUB FR

REACTIVE DYES
Introduction:
Reactive dyes are so called because their molecules react chemically with the polymers of
some fibres to form a covalent bond between the dye molecule and fibre polymer. Reactive
dyes are most readily used to dye cellulosic fibres like cotton, viscose etc. but it can be used
to dye synthetic Nylon, and natural protein fibres.

Cell-OH + HO- Cell- O-+ H2O

Cell- O-+ Dye-Cl Cell-O-Dye + Cl-
Where Cell-OH is the cellulose with a reactive hydroxyl group, Dye-Cl is the dye with its
reactive chlorine atom, and Cell-O-Dye, the dye linked to the cellulose by a covalent bond.
The role of the alkali is to cause acidic dissociation of some of the hydroxyl groups in the
cellulose, and the cellulosate ion (Cell-0- ) reacts with the dye.

General Dye Features:

W-D- Q RG X
W: Solubilising group / Auxochrome group (-NH2, -NH-CH3, -OH, -COOH, -NO2)
D: Chromogen
Q: Bridge link (-NH-, -NHCO-, -NHSO2-, -NCH3-)
X: Leaving Group (-Cl, -Br, -SH, -OCH)
RG: Reactive groups (Vinyl Sulphone, Monochlorotriazine, Dichlorotriazine)
The auxochrome/water solubilising group has the expected effect of improving the solubility,
since reactive dyes must be in solution for application to fibres. Auxochomes intensify the
hue of the dye molecule’s colour, makes the dye molecule more water soluble, and improves
the colourfastness properties of the dyed or printed fibre.

The bridging group links the chromogen and the fibre-reactive group. Frequently the bridging
group is an amino, -NH-, group. This is usually for convenience rather than for any specific
purpose.

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The reactive group is the only part of the molecule able to react with the fibre.

Properties of Reactive Dyes:

 Dyes are soluble in water and anionic in nature.
 Makes covalent bonds with the fibre.
 A certain amount of dye is hydrolysed during dyeing (10-60%).
 Dyeing is carried out in alkaline conditions (PH = 10.5-12).
 Fastness to wash, rubbing, light, and perspiration are generally good.
 Easily applicable to cellulose as well as protein fibres (Wool and Silk).
 Comparatively cheap.
 Al kinds of shades are found.
 The mechanism of reaction of reactive dyes with cellulose is generally classified
into two types-
 Nucleophilic addition reaction (Vinyl sulphone).

Dye-SO2-CH =CH2 + Cell-OH Dye-SO2-CH2-CH2-O- Cell

 Nucleophilic substitution reaction (Monochlorotriazine).

Cell- O- + Dye-Cl Cell-O-Dye + Cl-

Classification of Reactive dyes:
Classification of reactive dyes based on functional group:
1. Mono - functional
2. Bi - functional
a) Homo - bi functional b) Hetero - bi functional
3. Tri – functional
4. Tetra – functional
5. Penta – functional

Mono functional reactive dyes: F

Cl Cl

N N N N
N N

N N
Dye-HN NHR Dye-HN NHR
Cl
N
Dye-HN Cl

DCT (Dichlorotriazine) MCT (Monochlorotriazine) MFT (Monofluorotriazine)

Cl Cl

Cl Cl
N N
Dye-SO2-CH=CH2
N N
Dye-HN Cl Dye-HN F

TCP (Trichloropyrimidine) DFCP (Difluorochloropyrimidine) Vinylsulphone (VS)

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Classification of Reactive Dyes based on Application:

The reactive groups of the various types of reactive dyes have different chemical structures
and show a wide range of reactivity. They were originally divided into cold- and hot-dyeing
types but many current ranges would be better called warm dyeing. The most reactive types,
such as DCT reactive dyes only require a weak alkali such as NaHCO3 or Na2CO3 for
fixation. The less reactive types such as MCT dyes need stronger alkalis such as Na2CO3 plus
NaOH.
Dyes Brand Fixation Temp˚ C
Cold <40
Warm 40-80
Hot >80

Classification of Reactive Dyes based on Reactivity:

Type PH
Highly Reactive Dyes 10
Medium Reactive Dyes 10.5-11
Lower Reactive Dyes 11-12

Recipe:
Reactive Dye(s) : 2% OWF (on the weight of fabric)
Wetting Agent : 1 g/L
Sequestering Agent : 1.5 g/L
Anti-creasing Agent : 0.75 g/L
Levelling Agent : 1.5 g/L
Anti-Foaming Agent : 0.5 g/L
Salt (NaCl/Na2SO4) : 40 g/L
Soda Ash (Na2CO3)/NaOH/Mixed (PH=11) : 5 g/L
M:L : 1:10
Temperature : 60°C

The Three-Step Exhaust Dyeing Process:

1. The Initial Exhaustion Phase:
Dyeing is started in neutral solution so that there is little likelihood of the dye reacting with
the cellulose. During this stage of dyeing, some reactive dye will be absorbed by the fibres,
the amount depending upon its substantivity power. This dye is capable of promoting level
dyeing. Sodium chloride or sulphate will often be present initially or be added gradually to
the dye bath during this phase to promote exhaustion.
2. The Fixation Phase:
After the initial exhaustion phase, the PH of the dye bath is increased by complete or gradual
addition of the appropriate type and amount of alkali. This causes dissociation of some of the
hydroxyl groups in the cellulose and the nucleophilic cellulosate ions began to react with the

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dye. The fixation process then results in additional dye absorption, to re-establish the dyeing
equilibrium. Dye absorption from solution and reaction with the fibre then progress until no
further dye is taken up.
3. The Post-Dyeing Washing-off:
The rinsed dyeing contains dye bonded to the cellulose, absorbed but unreacted dye, as well
as hydrolysed dye. There will also be residual salt and alkali. These are removed by
successive rinsing in cold and then warm water. As much unfixed dye as possible must be
washed out of the dyeing. If this is not done, desorption of this dye during washing by the
consumer can cause staining of other material in the wash. Some unfixed dye is eliminated
during the initial rinsing that removes salt and alkali. Thorough washing of the dyeing using a
boiling detergent solution (soaping) eliminates the remainder. Soaping must often be repeated
for deep dyeings.
Colour Fastness properties of reactive dyes:

Colour fastness to wash: Reactive dyes on cellulosic fibres give dyeings with good to very
good fastness to washing and other wet processes. Apparent inferior fastness to washing is
usually because of incomplete removal of unreacted and hydrolysed dye from the material by
washing after dyeing.
Colour fastness to light: Textile material coloured with reactive dye has a moderate to good
light fastness and a rating is about 5-6.There are some reactive dyes with only fair light
fastness.
Colour fastness to Perspiration: Reactive dyes have good perspiration fastness with rating
4-5.
Colour fastness to rubbing: Textiles dyed with reactive dyes have moderate rubbing
fastness. Perspiration is slightly acidic and may affect textile materials coloured with reactive
dyes and result in some fading.
Colour Fastness to chlorine:
When reactive dyes were first introduced, it was found that bleaches which contained
chlorine, adversely affected some of these dyes.

Problems/ Disadvantages in dyeing with Reactive Dyes:

o One of the major problems in exhaust dyeing with many reactive dyes is the rather
low level of fixation, particularly when using a high liquor ratio. Often less than 70%
of the original dye reacts with the fibre.
o Low level of fixation results in appreciable dye concentration in the dye house
effluent. This environmental problem is compounded if high salt concentrations are
also present.
o If the amount of unfixed dye remaining in the goods is significant, there is a risk of
the precipitated dye-auxiliary complex rubbing-off, particularly on wet abrasion.
o Dyeings with a few red DCT reactive dyes on cotton are prone to increased colour
bleeding because of the dye-fibre bond.

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o There is always a risk of anionic reactive dyes being precipitated by calcium,

magnesium or heavy metal ions in the water supply, or of the formation of insoluble
hydroxides of these metals under the alkaline dyeing conditions.
Trade Names of Reactive Dyes:

Trade Name Company Country

Procion I.C.I. UK
Cibacron Ciba-Geigy Switzerland
Drimarene Sandoz Switzerland
Livafix F.Bayer Germany
Remazol F.Hoechst Germany
Cavalite Dupont USA

Printing with Reactive Dyes

A) The Choice of Thickeners:

 Sodium alginate.
 Starch.
 CMC (Carboxy-methyl Cellulose).
 Natural gums.
 British gums.
 Gum Tragacanth, etc.

B) Fabric Preparation prior to printing:

 Fabric should be bleached or mercerized.
 Fabric should not be in neutral or slightly alkaline condition.
 No residual starch in the fabric.

C) Different process sequences of printing:

A) Steaming process (All in method):
Print with alkali Dry Steam Wash-off Dry
B) Dry heat process:
Print with alkali Dry Cure Wash-off Dry
C) Alkali-pad printing process (Two Phase Method):
Print Without alkali Dry Pad with Alkali Steaming
Wash-off Dry
D) Air Development process:
Print with alkali/ Print without alkali on alkali padded fabric Hang in
Air Wash-off Dry

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Steaming Process (All in Method):

Recipe:
Reactive Dyes : 10gm
Thickener (Sodium alginate) : 500g (6% Paste)
Urea : 200gm
Sodium bi-carbonate : 20gm
Sodium m-nitrobenzene sulphonate : 10gm
Water : 260gm
Total : 1 kg

Printing of Cotton fabric by Two Phase Method:

 The fabric is pre-treated.
 Printed with a paste containing only dye, thickener and water.
 After drying, passing through an alkaline solution of high electrolyte content.
 Fixing by steaming at about 120°C for 30-60 seconds without intermediate
drying.
 Then soaping and washing is carried out.

1. Recipe for print paste:

Reactive Dyes : 30-50gm
Thickener Paste (6% Na-Alginate) : 470-450gm
Water : 500g

Total : 1 kg

2. Recipe for pad-liquor (Treated with 70% pickup)

Common Salt (NaCl) : 150gm
Potassium Carbonate (K2CO3) : 100gm
Sodium Hydroxide (68°Tw) : 30ml
Water : 720ml

Total :1L