Reactive dyes

Among the different classes of dyes for the cellulosic fibres the reactive dyes are
the only ones that attach themselves to the fibres by covalent bonds and get
their name for the same reason. Reactive dyes have certain groups in their
molecules that are capable of forming of covalent linkages between carbon atom
of the dye ion and oxygen, nitrogen/sulpher atom of a hydroxyl, an amino or a
mercapto group respectively of the fibrous substrates. At this stage it is relevant
to consider the basic mechanisms of the dye fibre attachments that can be of
three types:

 Physical adsorption

 Mechanical retention and

 Chemical reaction

Chemical structure of Reactive dyes

After the success of procion dyes in 1953, all the major dyestuff manufacturers
begin investigating to find new reactive groups. In 1958 after going through their
wool dyes ranges, introduced Remazol dyes that formed the covalent bond by
“nucleophilic addition” reaction as indicated below:

(-HCl)

D-SO2CH2-CH2Cl = [D-SO2CH=CH2] + HO-Cell = D-SO 2CH2-

CH2OCell

These developments made the colour chemists think seriously, perhaps for the
first time, about the chemical structures of fibres especially of cellulosic fibres
and their role in dyeing mechanisms. In subsequent years all the major dye
manufacturers many new reactive groups. It is known that about 250 reactive
groups have been patent but only 20-30 have actually been marketed for both
cellulosic and protein fibres by cold as well as hot dyeing process.

The four distinct structural features of mono-functional reactive dye are

chromogen, the the reactive system, the bridging link and one or more
solubilising groups. The structure can be represented as:

W-D-Q-RG-X
Where D is the chromogen, W is the water-solubilising groups, Q the
bridging link, RG the reactive group and X the leaving group. Some reactive
groups are shown below:
 Reactive group Trade name manufacturer

D-SO2CH2-CH2-NR2 REMAZOL (HOECHST)

DYESTAR

D-NHCOCH2CH2OSO3H + PRIMAZINE (BASE)

D-NHCOCH = CH2Cl DYESTAR

Types of reactive dyes

Some other important according to market point of view types with their
structure are given below:

1. Sulphatoethyl sulphone dyes:

Vinyl sulphone dye (Remazol Brilliant Blue R, C.I. Reactive Blue 19)

2. Monochloro-s-triazine dyes:

Monochloro-s-triazine dye (Procion Red H-3B, C.I. Reactive Red 3)

 3. Bis (monochloro-s-triazine) dyes:

Bis (monochloro-s-triazine) dye (Procion Red HE-3B, C.I. Reactive Red 120)

The reactive dyes are the brightest dyes available for the cellulosic fibres and
have a full range of shades with very good wash and fairly high fastness
properties. These dyes offer a great flexibility in application methods with a wide
choice of equipment and process sequences and so have become very popular.
As a class, the reactive dyes are stable to peroxide bleaching and so are used for
dyeing cotton and viscose yarns to be employed as effect threads. Strong
reducing agents and chlorine however destroy the chromogens.

Hot And Cold Dyeing Brands

Cold Dyeing Brand:

Reactive Cold Brand Dyestuffs are fibre reactive dyes which form a
chemical linkage with Hydroxyl groups of Cellulose and thus give dyeing
and printing good fastness to wet treatments.

Hot Dyeing Brand:

He Dyes are Reactive Dyes for Cellulosic material and designed to give
high fixation by exhaust dyeing method when applied at the temperature
75ºC - 95ºC.
The other misconception that people have is that they assume the Hot
dye is more colour-fast than the Cold one because you have boiled the
colour in. This is not so. Cold dyes are more robust and colours will remain
brighter for longer than Hot dyes. The cooler process is not only a little
easier, it is also more lasting.

Cold reactive dyes are very reliable and used throughout the global
clothing and textile industries to permanently colour fabrics made from
plant fibres. The dyes react with the fibre on a molecular level to produce
a permanent bond that withstands wash after wash. The colour becomes
part of the fabric.

Methods of dyeing of reactive dyes

In the absence of alkalis, the reactive dyes behave like levelling class of direct
dyes but being of relatively smaller molecular size, are exhausted with higher
concentrations of electrolytes. Even then exhaustion of the dye is low and varies
between 50-75% in most classes. Reactive dyes can be applied by various
methods but choice of dyeing process depends on factors such as availability of
equipment, depth of shade, length of fabric and how much production is
required.

Methods of reactive dyeing:

 Batch process

 Semi-continuous process

 Continuous process

Here in Sapphire mills limited, dyeing process is limited to full continuous

method due to the limitations of equipment as well as it is the production
requirement.

Continuous process
Continuous dyeing is highly productive system in which basically the dye-padded
fabric is exposed to high temperature for a for a very short time, followed by
washing in a continuous washing range. The continuous dyeing equipment
requires considerable capital investment but with skilled organization and good
management. This system of production offers the advantages of high
productivity and lower labour and handling costs as compared with the batch
processing of an equal quantity of material. A number of fully continuous
methods are practiced in industry; their choice depending on the fastness
requirements, depth of shade, availability of reactive dyes that are extensively
used in industry.

I. Pad-dry-steam (for only light and medium depth shades)

 II. Pad-dry-chemical pad-steam

III. Pad-dry-thermofix

IV. EControl, pad-Humidity-fix or Drimafix/Pad-moist

In Sapphire mills ltd. only first two methods are being used.

Pad-Dry-Steam Method
In this process, the fabric is padded in a liquor containing dye, 10-20 g/l soda
ash, 10 g/l anti-reducing agent and 5-15 g/l migration inhibitor and then dried at
100-130’C. Penetration into fibre and fixation of the dye is accomplished by
steam for 3-5 minuets at 102-104’C. For very light shades even the intermediate
drying is excluded. Washing off the hydrolysed dye and chemicals is done by the
usual washing process and is discussed in high degree fixation of reactive dyes.

Pad-Dry-Chemical Pad-Steam
This system gives most satisfactory results. The fabric is padded with dye, dried,
padded again in alkali, steamed and washed. As no alkali is added in dye bath,
the stock solution remains stable over long periods and then also be applied at
high temperatures up to 50’C so as to reduce exhaustion during the padding
stage and thus avoid the tailing defect.

The fabric is padded in the dye-liquor containing a wetting agent and an anti-
migration like sodium alginate and dried in a hot air drier. The dried and cooled
fabric is again padded in a chemical pad containing 200-250g/l of electrolyte and
5-30ml/l of 30% caustic soda solution. After chemical padding up to 70-80% pick
up, the fabric is steamed that may last for 30 seconds to 2 minuets depending
upon depth of the shade. The unfixed dye is removed as usual in a washing
range.

Washing off after dyeing

It has been learnt from the research studies that in the first cold rinse very little
dye of medium to high affinities is removed because substantivity of the dye
increases as temperature of the bath falls. And this happens in spite of the fall of
concentration of the electrolyte from 120g/l to 36g/l. the second cold rinse
reduces 50% of the absorbed hydrolysed dye while the electrolyte concentration
falls to about 11g/l. the following hot washes are very efficient in desorption of
loose dye. Proper soaping after treatments then almost also completely remove
the remaining hydrolysed dye. The usual sequence is given below:

Rinse in overflowing cold water 2 cisterns.

Rinse in boiling water 2 cisterns.

Soap at boil with 1-2g/l and

2g/l soda ash 2 cisterns.

Rinse in hot water 1 cistern.

 Rinse in cold water 1 cistern.

Advantages and Disadvantages

Advantages:

• Full Colour Gamut

• Brilliant, bright colours
• Covalent fixation à high Wash Fastness (WF)
• Varying relativities
– Various temperatures including low energy (cold dyeing)
• Various methods of application
• Inexpensive to apply (but dyes expensive)

Disadvantages:

• Incomplete fixation (problem with hydrolysis)

• Need for wash-off (for high WF)
• Need for high concentrations of salt
– Affect natural balance of watercourses
• High pH
• Some dyes are “AOX” – potentially harmful to the environment