CONTENTS

1 HISTORY ......................................................................................................................... 3
2 INTRODUCTION .............................................................................................................. 3
3 PROPERTIES .................................................................................................................... 4
4 POPULARITY OF REACTIVE DYE ....................................................................................... 5
5 ADVANTAGES OF REACTIVE DYES .................................................................................... 5
6 DISADVANTAGES OF REACTIVE DYES............................................................................... 6
7 STRUCTURE .................................................................................................................... 6
8 CHARACTERISTICS OF REACTIVE GROUP OF DYE .............................................................. 8
9 CLASSIFICATION.............................................................................................................. 9
9.1 CLASSIFICATION OF REACTIVE DYE ACCORDING TO DYEING TEMPERATURE ........................................ 9
9.2 CLASSIFICATION OF REACTIVE DYE ACCORDING TO REACTIVITY........................................................ 9
9.3 CLASSIFICATION OF REACTIVE DYE ACCORDING TO REACTIVE GROUP ............................................... 9
9.4 CLASSIFICATION OF REACTIVE DYE ACCORDING TO FUNCTIONAL GROUP ........................................ 10
9.4.1 1. Monofunctional Reactive dye: ................................................................................ 10
9.4.2 2. Bi-functional Reactive Dye: ..................................................................................... 14
9.5 CLASSIFICATION OF REACTIVE DYE ACCORDING TO CONTROL PARAMETER ...................................... 16
10 TYPICAL TRADE NAMES OF REACTIVE DYES ................................................................... 18
11 REACTION MECHANISM OF REACTIVE DYES .................................................................. 18
11.1 REACTION MECHANISM OF NEUCLEOPHILIC SUBSTITUTION .......................................................... 18
11.2 REACTION MECHANISM OF NUCLEOPHILIC ADDITION .................................................................. 19
11.3 COLD BRAND REACTIVE DYE REACTION MECHANISM ................................................................. 19
11.4 HOT BRAND REACTIVE DYE REACTION MECHANISM ................................................................... 20
11.5 REACTIVE DYE REACTION WITH COTTON AND WATER ................................................................ 20
12 FACTORS TO BE CONSIDERED FOR REACTIVE DYE .......................................................... 21
13 FUNCTION OF CHEMICALS/ASSISTANTS USED IN REACTIVE DYEING .............................. 22
14 FACTORS GOVERNING REACTIVE DYE UPTAKE ............................................................... 22
15 BASIC PRINCIPLE OF REACTIVE DYEING WITH STEPS ...................................................... 23
16 MECHANISM OF REACTIVE DYEING ............................................................................... 24
17 HYDROLYSIS OF REACTIVE DYES .................................................................................... 25
17.1 MINIMIZING HYDROLYSIS OF REACTIVE DYE .............................................................................. 27
18 APPLICATION OPTIONS OF REACTIVE DYE ..................................................................... 27
19 DYEING OF COTTON MATERIAL WITH REACTIVE DYE ..................................................... 28
19.1 RECIPE FOR COLD BRAND REACTIVE DYES ................................................................................. 28
19.2 RECIPE FOR HOT BRAND REACTIVE DYES .................................................................................. 29
19.3 PROCEDURE ....................................................................................................................... 29
20 COTTON DYEING BY REACTIVE DYE - BATCH METHOD ................................................... 29
20.1 PROCION-M RECIPE .......................................................................................................... 29
20.2 PROCION-M DYEING PROCESS ............................................................................................. 29
20.3 CIBACRON-E RECIPE .......................................................................................................... 30
20.4 CIBACRON-E DYEING PROCESS............................................................................................. 30
21 COTTON DYEING BY REACTIVE DYE - CONTINUOUS METHOD ........................................ 30
21.1 PAD STEAM METHOD RECIPE ................................................................................................ 30
21.2 PAD STEAM METHOD DYEING PROCESS ................................................................................... 30
21.3 PAD THERMO FIXATION METHOD RECIPE ................................................................................. 31
21.4 PAD THERMO FIXATION METHOD DYEING PROCESS ................................................................... 31
22 COTTON DYEING BY REACTIVE DYE - SEMI CONTINUOUS METHOD ................................ 31
22.1 PAD ROLL METHOD RECIPE ................................................................................................... 31
22.2 PAD ROLL METHOD DYEING PROCESS ..................................................................................... 31
22.3 PAD JIGGER METHOD RECIPE................................................................................................. 32
22.4 PAD JIGGER DYEING PROCESS ................................................................................................ 32
23 AFTER TREATMENT OF REACTIVE DYES ......................................................................... 32
24 RIGHT FIRST TIME DYEING (RFT).................................................................................... 33
24.1 NECESSITY OF RFT DYEING.................................................................................................... 33
25 STRIPPING OF REACTIVE DYES ....................................................................................... 34
25.1 PARTIAL STRIPPING OF REACTIVE DYES .................................................................................... 34
25.2 FULL STRIPPING OF REACTIVE DYES ......................................................................................... 34
26 COTTON FABRIC PRINTING WITH REACTIVE DYE ............................................................ 35
27 WOOL FABRIC PRINTING WITH REACTIVE DYE ............................................................... 36
27.1 DIRECT STYLE PRINTING RECIPE .............................................................................................. 36
27.2 PRINTING PROCESS .............................................................................................................. 36
28 SOME QUESTIONS ........................................................................................................ 36
 Reactive dye
1 HISTORY
Reactive dyes are developed in the 1950s. In 1895, Cross and Bevan, two scientists, considered
covalent bonding with textile fibers. Then in 1952, a scientist named Guthrie provided an
important explanation for the reaction of dye molecules with fiber. Based on these, the British
ICI company succeeded in inventing the first reactive color in 1956. In 1956, the company
commercialized reactive dyes and marketed them, as well as many companies.

2 INTRODUCTION
The dye that contains reactive group in its structure and this reactive group creates covalent link
with the fiber to act as an integral part of the fiber is called reactive dye. Reactive dyes are mainly
applied on cellulosic fibres such as cotton, viscose rayon, cuprammonium rayon, Wool, Nylon etc.
Generally, these dyes are easily applied on cellulosic fibres and can be directly dyed from simple
solution in water with alkali. These dyes chemically react with fibre forming covalent bond. The
dye forms a covalent link with fiber and becomes a part of the fiber. Such dye molecules have
some reactive groups, which react with the functional groups of fibers, such as the OH group of
cellulose and the NH2 group of protein fibers. This is why all these dyes are called “fiber reactive
dyes”.
3 PROPERTIES
• During the dyeing process, the reactive group of the dye forms a covalent bond with the
fiber and a portion of the fiber remains in the account.
• These dyes are less substantive than direct dye. So, requires more salt for exhaustion.
• It has a high wet fastness. However, its level depends on the stability of the covalent bond.
• Brightness and rubbing fastness of this dye are comparatively higher than VAT and Azoic
dye.
• They have excellent light fastness with a rating of about 6.
• It is commonly used to dye cellulose, regenerated cellulose and protein fibers.
• Reactive dyes are highly soluble in water. Solubility increases with the addition of urea.
• Reactive dyes are anionic in nature.
• Dyeing process is usually done in an alkaline medium.
• Dyeing process require less time and temperature.
• Cold brand has higher affinity for cotton, so suitable for exhaust dyeing.
 • Hot brand and Remazol are suitable for padding and printing due to their poor affinity for
cotton.
• Reactive dyes show Excellent washing fastness (Except cold brands) & light fastness.
• Reactive dyes have good perspiration fastness with rating 4-5.
• Reactive dyes show poor bleaching fastness. (Bleaching Powder).
• There is no loss of dye in gas fading and dry cleaning.
• This dye is relatively cheap.
• All types of shades are available by the reactive dye.
• Reactive dyes are found in powder, paste and liquid form.
• Reactive dye molecules are not as long as those of direct dye. For this reason, short
molecule has good clarity and brightness of hue, easy penetration with good levelling.
• Reactive dyes have very stable electron arrangement and might protect against the UV
ray.

4 POPULARITY OF REACTIVE DYE

Reactive dyes are superior to direct dyes in the following aspects:
1. Ability to produce bright shades of wide range.
2. High leveling quality.
3. Good washing fastness. (Rating 4-5)
4. Very good light fastness. (Rating 6)
5. Good rubbing and perspiration fastness properties (rating 4-5)
Again, it is superior to vat dyes in the following aspects:
1. Simple dyeing method.

2. Low temperature dyeing (below 80°c)

3. Simple dye molecule structure and easily soluble in water compare to vat dye.
4. Cheap.
Again, its dyeing process is fast and gives brighter shades than metallized azo dyes. For the above
reasons reactive dyes are more popular.

5 ADVANTAGES OF REACTIVE DYES

1. High color yield: Reactive dyes have a high degree of fixation on the fabric, resulting in
bright and vibrant colors.
 2. Good wash and light fastness: Reactive dyes are highly resistant to fading or bleeding,
even after repeated washing or exposure to sunlight.
3. Wide color range: Reactive dyes offer a broad range of colors, from bright and bold to
subtle and pastel shades.
4. Environmentally friendly: Reactive dyes are relatively safe to use and produce minimal
waste.
5. Various temperature dyeing: Reactive dyes can be used at both low and high temperature
according to need.

6 DISADVANTAGES OF REACTIVE DYES

• Incomplete fixation (problem with hydrolysis)
• Need for wash-off (for high WF)
• Need for high concentrations of salt
• Color is not easily removed by effluent treatment processes and in many cases, the dyes
are not readily biodegradable

7 STRUCTURE

S = Solubilising Group like SO3Na, or COONa, or combination of both

C = Chromophoric Group, responsible for affinity and diffusion of dye
B = Bridging Group, attach the reactive system to chromogen C
X = Reactive system, reacts with the functional group of fibre forming homo-polar bond
 1. Chromophore: N=N
2. Solubilizing group: SO3Na
3. Bridging group: -NH-
4. Reactive group
5. Leaving group: Cl, F etc.
Four characteristic features in the system:

• Chromophore grouping: contributing the color & much of the substantivity to cellulose.
• The reactive system: enabling the dye to react with the hydroxyl groups in cellulose.
• A bridging group: that links the reactive system to chromophore.
• One or more solubilizing groups: usually sulphonic or substituents attached to chromophore.

Where, D=Dye. The above dye is a triazine reactive dye in which chlorine is the reactive site.
8 CHARACTERISTICS OF REACTIVE GROUP OF DYE
1. Reactive groups of dyes do not contribute to the color of dye. Color is only imparted by

chromophore group of the structure.

2. The reactivity of vinyl sulphone group is less than that of halogen group.
3. If no of reactive group increases, binding also increases depending on dye structure.
4. Exhaustion and fixation of reactive dye is more than 80%.
5. Molecular wt of reactive group 69-211 gm/mole.
6. Bond energy of halogen groups is as below:
F (Fluorine) - 102 Kcal /gm
Cl (Chlorine) - 74 K cal / gm
Br (Bromine) - 64 K cal / gm
I (Iodine) - 56 K cal / gm
7. According to reactivity, Iodine is 1st, but hydrolysis is high.
8. Chlorine is medium and it is preferred because it is cheap as well as not so high or lower
reactive.
9. Reactivity of Fluorine is the least, and its rate of hydrolysis also less but takes more time.
10. Reactivity of vinyl sulphone group increases with increasing temperature and PH.
11. If no. reactive groups in dye molecule increase, then cost increases.
12. Sulphonate group has more solubility compare to other auxochrome groups.
13. Generally low molecular weight dyes are of hot brand (i.e. less reactive).
14. Less affinity dyes are used for pad method.
9 CLASSIFICATION

9.1 CLASSIFICATION OF REACTIVE DYE ACCORDING TO DYEING TEMPERATURE

1. Cold Brand: These types of dyes contain reactive group of high reactivity. So, dyeing can
be done at lower temperature, i.e. 35 to 45 C. Example: Procion M, Livafix E etc.
2. Medium Brand: These types of dyes contain reactive group of moderate reactivity.
Temperature is between 55 to 65 C. Example: Remazol, Livafix etc.
3. Hot Brand: These types of dyes contain reactive group of least reactivity. So, high
temperature is required for dyeing, i.e. 75 to 90 C. Example: Procion H, Cibacron etc.

9.2 CLASSIFICATION OF REACTIVE DYE ACCORDING TO REACTIVITY

1. Lower Reactive Dye: PH is maintained at 12 to 12.5 by using NaOH in the dye bath.
Example – Premazine.
2. Medium Reactive Dye: PH is maintained at 11 to 12 by using Na2CO3 in the dye bath.
Example - Levafix E (BAY).
3. Higher Reactive Dye: PH is maintained at 10 to 11 by using NaHCO3 in the dye bath.
Example - Procion M.

9.3 CLASSIFICATION OF REACTIVE DYE ACCORDING TO REACTIVE GROUP

Basically two types-
1. Heterocycles containing halogen substituents.
2. Active Vinyl compounds
1. Heterocycles containing halogen substituents:
(a) Triazine group: For example- Procion, Cibacron etc.
(b) Pyrimidine group: For example- Reactone.

(c) Quinoxaline group: For example- Levafix.

2. Active Vinyl compounds:

• Vinyl Sulphone (D-SO2-CH2-CH2-) Ex: Ramazol (Hoechst)
• Vinyl Sulphonamide (D-SO2-NH-CH2-CH2-) Ex. Levafix (Bayer AG)
• Vinyl acrylamide (D-NH-CO-CH2-CH2-) Ex: Primazine (BASF)

9.4 CLASSIFICATION OF REACTIVE DYE ACCORDING TO FUNCTIONAL GROUP

According to functional group, Monofunctional & Bifunctional Reactive dyes are available.

9.4.1 1. Monofunctional Reactive dye:

Contains only one possible reactive center. Halogen substituent in the amino halo-triazine dyes
or activated terminal carbon atom in the vinyl sulphone system. Examples are given below-
1. Di Chlorotriazine Dye-

• Highly reactive
• Temp (30-40)°C
• Pad -batch dyeing
• Relatively small chromogens are preferred to ensure mobility.
• Suitable for bright dyeing.
• CI Reactive Red I
2. Amino-Chloro-Triazine Dye:
 • 2-amino 4-chloro derivative
• Temp-80°C
• PH – 11
• CI Reactive Red 3
3. Amino-Fluoro Triazine Dye:
• More reactive than Amino-chloro-triazine dye.
• Cibacron F (CGY)
4. Tri-Chloro-Pyrimidine Dyes:
 • Less activation of Chloro substituents.
• Temp – 100°C
• Stable bonding
5. Di-Chloro-Quinoxaline Dye:
 • Relatively higher than Di chloro-triazine & Di-fluoro-pyrimidine
• Temp-50°C
• Levafix E (BAY)

9.4.2 2. Bi-functional Reactive Dye:

From around 1970, concept on dyes of combined two reactive system developed. Some typical
examples with criteria are given below-
1. Bis (Amino-Chloro-Triazine) Dye:
 Fig: CI reactive Blue 171 [Procion Navy H-ER]

• Homo Bi-functional dye.

• High substantivity allows them to achieve excellent exhaustion at 80°C.
• Fixation 70-80%
• High temp application conditions ensure good good levelling.
• High fixation leads to:
• Better utilization
• Less hydrolyzation
• less discoloration of the element
• Rate of removal of unfixed dye is slow.
2. Bis (Amino-Nicotino-Triazine) Dye:
• Homo Bi-functional dye.
• Amino-chloro-triazine + 3° amine
• Quaternary NH4 derivative.
• polarization of C-N increases.
• More reactive.
• PET/Cotton blend dying suitable, as >1000C dyeing recommended.
• N,N-dimethylhydrazine, pyridine.
• Kayacelon React Red CN-3B.
• Procion Red H-E3B
3. Aminochlorotriazine-Sulphatoethyl Sulphone Dye:

Fig: Sumifix Supra Brilliant Red 2BF(NSK)

• Hetero Bi-functional dye.

• Di chlorotriazine dye + arylamine containing 2-sulphatoethyl sulphone → Bifunctional
dye.
• Capable of reacting via mono-chloro-triazine moiety or a vinyl sulphone group.
• Sumifix Supra Brilliant Red 2BF (NSK).
• Vinyl Sulphone group ensures most of the fixation.
• Triazine bridging residue contributes higher substantivity.
• Temperature: 50-80°C
• Less affected by electrolyte and liquor Ratio.
• Low temperature suits VS (Vinyl Sulphone).
• High temperature suits CTR (Chlorotriazine).

9.5 CLASSIFICATION OF REACTIVE DYE ACCORDING TO CONTROL PARAMETER

Group-1: Alkali controllable reactive dye:

• Temp of fixation: 40-60°C

• Low exhaustion before alkali add.
• Alkali addition influence high reactivity.
 • Level dyeing to be taken care of by controlled dosage rate.
• Example: Di-chlorotriazine, Chloro-difluoro Pyrimidine, Di-chloro-quinoxaline, vinyl-
sulphone etc.
Group-2: Salt controllable reactive dye:
• Temp of fixation: 80 – 100°C
• High exhaustion at neutral PH
• Level dyeing by adding salt. Portion wise or controlled rate of dosage.
• Low reactive.
• Example: Tri-chloro-pyrimidine, Amino-chlorotriazine etc.
Group-3: Temperature controllable reactive dye:
• Temperature greater than boil.
• Alkali not required.
• Self levelling.
• Time rise rate needs to control.
• Example: Kayacelon React (KYK) etc.
10 TYPICAL TRADE NAMES OF REACTIVE DYES
1. Remazol
2. Procion
3. Cibacron
4. Novacron
5. Bezaktiv
6. Lebafix
7. Sumafix
8. Drimarene
9. Dystar
10. Lanaset

11 REACTION MECHANISM OF REACTIVE DYES

Two types of reactions occur. They are-
1. Nucleophilic substitution: Substitution of chlorine, fluorine, methyl sulphone or nicotinyl
leaving group happens by an adjacent nitrogen atom in a heterocyclic ring.
2. Nucleophilic Addition: Nucleophilic addition of cellulosate ion(cell-O–) and H+ ion to a C=C
(carbon-carbon double bond) happens by an adjacent electron attracting sulphone group.

11.1 REACTION MECHANISM OF NEUCLEOPHILIC SUBSTITUTION

Nitrogen containing heterocyclic rings bearing halogens substituents undergo nucleophilic
substitution. The hetero atoms in the aryl ring activate the system for nucleophilic attack because
of their electronegativity. The attacking nucleophilic is cellulosate ion. Thus fixation occurs.
 Cell–OH + HO– ⇒ Cell–O– + H2O
Cell–O–+ Dye–Cl ⇒ Cell–O–Dye + Cl–

11.2 REACTION MECHANISM OF NUCLEOPHILIC ADDITION

Nucleophilic addition is applicable for VS(vinyl sulphone) compounds. Alkaline 1,2- elimination of
Precursor (2-sulphato ethyl sulphone) is done to release the reactive vinyl sulphone system.
SO2-CH2-CH2O-SO3Na + NaOH→ -SO2-CH=CH2 + Na2SO4 + H2O
(sulphato ethyl sulphone) (Reactive vinyl sulphone)
During nucleophilic addition reaction, carbon-carbon double bond is polarized by the powerfully
electron-attracting sulphone group. This polarization confers a positive character on the terminal
carbon atom, favoring nucleophilic addition of cellulosate ion, leading to fixation.
Cell–O–+ Dye–SO2–CH=CH2 ⇒ Dye–SO2–CH=CH2–O–Cell

11.3 COLD BRAND REACTIVE DYE REACTION MECHANISM

▪ Cold brand reactive dye, being highly reactive due to presence of two chlorine atoms, it
is more susceptible to hydrolysis and also possessing high fixation rate.
▪ One chlorine atom of dye attach to the functional group of fibre, while another one reacts
with water.
 ▪ Reaction with water results into hydrolysis of dye, and so the wash fastness is poor as
partially hydrolysed dye can not be removed from the dyed cotton.

11.4 HOT BRAND REACTIVE DYE REACTION MECHANISM

In hot brand reactive dye, only single chlorine atom is present, so it can either react with cellulose
or with water. But do not stain adjacent ground.

11.5 REACTIVE DYE REACTION WITH COTTON AND WATER

▪ Hydroxyl group present in cotton reacts with reactive dye with the liberation of acid, even
at neutral pH.
▪ To increase the fixation, liberated acid must be neutralize with the addition of alkali.
▪ Hydrolysis process also produces acid, while reacting with dye.
▪ Rate of hydrolysis is very less to the rate of dyeing, with strictly controlling parameters of
efficient dyeing.
 ▪ Remazol dyes also react with cotton and water in same manner.

▪ Hot brand and Remazol react with cotton at primary hydroxyl group at C6 position, while
cold brand reacts with two different hydroxyl groups at a time.

12 FACTORS TO BE CONSIDERED FOR REACTIVE DYE

1. Dyeing Temperature:
Dyeing temperature 200C-350C is recommended for most reactive dyes. But reactive dyes
in sodium bicarbonate alkali provide maximum color value at a temperature of 50°C-60°C.
2. Concentration of Electrolytes:
The concentration of an adequate amount of exhaustion has to be changed in proportion
to the liquor. That is, if the liquor ratio decreases, the amount of salt also has to decrease.
It has been found that 10 g/liter of salt is required for pale shade. But for medium or deep
shade this amount should be increased up to 20 g/liter to 30 g/liter.
3. Time of Dyeing:
Generally in a dye bath dye is divided into two parts. Salt is also added in two parts. Then
20-30 minutes of exhaustion occurs. Then alkali is added and continuous dyeing is done
for 30-90 minutes. The time of dyeing is decided based on the depth of the shade and the
reactivity of the dye. Requires more dyeing time for relatively deep shade.
4. Liquor Ratio:
When the liquid ratio is low, both exhaustion and fixation occur at a slightly increased
rate. In this case, the lower amount of salt is the optimum color. In addition to dye, salt,
and alkali, wetting, defoaming and mild oxidant (m-nitrobenzene sulphonate) are added
to the dye bath.
5. PH of the Dye Bath:
It helps to ionize the dye molecule but at a higher pH, the ionization decreases. As the
temperature of the dye bath increases, the pH value decreases. For most dye, the pH value
is kept at 10.8-11.
13 FUNCTION OF CHEMICALS/ASSISTANTS USED IN REACTIVE DYEING
• Salts: Due to the high absorption capacity of salt towards the water, the salt falls on the
dyestuff as soon as it is added to the water. It spreads the dye evenly everywhere.
As a salt, Na2SO4 or NaCl is used widely. The salts do the following things –
a. It neutralizes the electro-negativity of fiber surface when immersed in solution
(chemistry)
b. Salts are used to increase the affinity of dye to fiber.
c. It puts extra energy to push the dye molecule inside the fiber polymer, i.e. increases
absorption of dye.
d. It decreases the hydrolysis rate of dyes.
The amount of salt used depends upon the shade required.
For light shade : 20 – 30 gm/lt.
For medium shade : 30 – 60 gm/lt.
For dark shade : 60 -100 gm/lt.
• Alkali: Soda Ash, Sodium Hydroxide or Sodium Bicarbonate are used as alkali. It acts as a
fixing agent. After the product is dyed, it helps the product to hold the dye.
Alkali is used for the following purposes –
a. It is used as a fixing agent.
b. Alkali is used to maintain proper PH in dyebath and this alkaline condition must be
maintained properly to create the covalent bond between dye and fiber. Without alkali
no dyeing will take place.
• Urea: It plays an important role in making the dye heavier or lighter. More urea is for
heavy coloring and less urea is for light coloring.
• Sodium Alginate: It is used to inhibit the migration of dye molecules. This means that after
dyeing the cloth, a small amount of adhesive sodium alginate is used to prevent the dye
from moving from one place to another.
• Soaping: Soaping increases the brightness of the color. Soaping also eliminates floating
color.

14 FACTORS GOVERNING REACTIVE DYE UPTAKE

1. Linear density of fiber.
2. Reactivity ratio.
3. Substantivity ratio.
4. Diffusion co-efficient of dye in the substate.
5. Liquor ratio: Reactive dyeing process is typically maintained in the range of 1:5 to 1:20
(Material to Liquor ratio).
 6. Surface area of substrate available for absorption of dye.
7. PH of dye bath: Reactive dyes falls within the range of 10 to 11.5.
8. The concentration of electrolyte, comprising common salt and Glauber’s salt, may vary
between 20-100 g/L, depends on the desired shade, ranging from 0.1% to 5.0%.
9. The temperature during dyeing plays a crucial role, as higher temperatures lead to
increased hydrolysis. Dyeing is conducted within the temperature range of 40°C to 100°C.
10. Dyeing time: The duration of the dyeing process is a key factor, with an increase in dyeing
time correlating with elevated hydrolysis. Exhaustion of the dye occurs within a
timeframe of 20-30 minutes.

15 BASIC PRINCIPLE OF REACTIVE DYEING WITH STEPS

1. Dyeing commenced in neutral solution, often in presence of salt.
2. Appropriate alkali added to increase PH, initiates dye-fiber reaction.
3. -OH (hydroxyl groups) of cellulose are weakly acidic and absorption of hydroxide ion
causes some dissociation, forming cellulosate ions, which react with dye by nucleophilic
addition or substitution.
4. Lower the reactivity, higher the temperature (hot brand) & higher the final PH
5. Hydroxide ions also react with reactive group as like as cellulosate ion.
6. This produces hydrolyzed dye.
 7. Although hydrolysis is slower, still affects fixation.
8. Through washing requires for removal of unfixed and hydrolyzed dye.
9. Rinsing (cold & warm), soaping, warm rinsing done.

16 MECHANISM OF REACTIVE DYEING

Reactive dyeing unfolds through a three-stage mechanism:

1. Dye Absorption or Exhaustion:

The initial stage involves immersing the fiber in a dye liquor containing an electrolyte, typically
NaCl. This addition of electrolyte serves to facilitate the exhaustion of dye. By neutralizing the
negative charge on the fiber surface, the electrolyte imparts extra energy, enhancing the
absorption of dye onto the textile material.
2. Fixation:
Fixation denotes the crucial reaction between the reactive group of the dye and the terminal –
OH or -NH2 group of the fiber. This interaction forms a robust covalent bond with the fiber and
is a pivotal phase controlled by maintaining the appropriate pH through the addition of alkali.
The choice of alkali, such as caustic soda, soda ash, or NaHCO3, depends on the reactivity of the
dye, acting as a dye-fixing agent. The reaction during this stage is illustrated below:

3. Wash-Off:
Upon completion of dyeing, thorough washing becomes imperative to eliminate excess,
hydrolyzed and unfixed dyes from the material surface. This step is essential for achieving
uniform dyeing and ensuring good wash-fastness. A sequence of hot wash, cold wash, and soap
solution wash is employed to accomplish this cleansing process. A batch washing off might
include: A cold-water wash at 25 to 60 C. A hot water wash at 60 to 80 C. Scouring with anionic
surfactant at 80 to 90 C. All this is followed by hot and then cold water washing.

17 HYDROLYSIS OF REACTIVE DYES

The fatal property of reactive dye is hydrolysis. Under alkaline condition reactive dyes react with
hydroxyl group of cellulose. But the reactive group of such dyes may react with water as the
increasing temperature which simply referred as hydrolysis. After hydrolysis the dyes cannot
react with fiber. Thus, hydrolysis increases the wastage of dyes.
1. Hydrolysis of halogen containing reactive dye
Dye – Cl + H – OH → Dye – OH + HCl
2. Hydrolysis of activated vinyl compound containing reactive dye
Dye – SO2 – CH2 – CH2 – O – SO3H + H – OH → Dye – SO2 – CH2 – CH2 – OH + H2SO
1. During Nucleophilic substitution, the nucleophile can be either cellulosate ion or
hydroxide ion (from water).

Fig: Partially hydrolyzed dye

2. During Nucleophilic addition,

Fig: Hydrolyzed dye

Reactive dyes are a type of dye that chemically react with the fibers of textiles to form a covalent
bond, resulting in a strong and permanent color. These dyes are widely used for dyeing natural
and synthetic fibers such as cotton, wool, silk, and polyester.
Hydrolysis of reactive dyes occurs when the dye molecule is broken down by water, resulting in
the release of the dye molecule from the textile fiber. This process can occur due to several
reasons, including exposure to high temperatures, acidic or alkaline conditions, or prolonged
exposure to water.
The hydrolysis of reactive dyes can result in several negative effects, including:
1. Fading of the color: The hydrolysis of the dye molecule can cause the color of the textile
to fade over time.
2. Reduced wash fastness: Hydrolyzed dyes are more easily removed from the textile during
washing, resulting in reduced wash fastness.
3. Staining of other textiles: Hydrolyzed dyes can transfer to other textiles during washing,
resulting in staining.
To prevent the hydrolysis of reactive dyes, it is important to use proper dyeing techniques and to
avoid exposing the textiles to extreme conditions. Additionally, using appropriate washing and
care instructions can help to maintain the color and wash fastness of the textiles.

17.1 MINIMIZING HYDROLYSIS OF REACTIVE DYE

Hydrolysis of reactive dyes can be minimized during dyeing if it is done in two stages –

1. The dyeing is first started from aqueous medium under neutral conditions when the dye does not react
either with fiber or with water.

2. The salt is added to exhaust the dye on to the fiber in two or three portions.

3. Dye migration is carried out in fiber polymer chain before adding alkali (fixing chemical)

3. Then the second step is carried out by adding alkali.

4. Since the exhausted dye is already in the fibre, it is more likely that exhausted dye reacts with fiber in
preference to water.

5.But the dyes in the dye bath react with water which has no affinity to fibers. Thus, the hydrolysis of
reactive dye can be minimized.

18 APPLICATION OPTIONS OF REACTIVE DYE

1. Continuous Method
 i) Pad Thermofix
ii) Pad Steam
iii) Pad Dry
2. Semi Continuous Method
i) Pad Batch
ii) Pad Roll
iii) Pad Jig
3. Discontinuous Method
i) Conventional Method
ii) Exhaust or Constant temperature Method
iii) High temperature Method
iv) Hot Critical Method
4. Batch wise exhaustion – Winch, Jet, Package & Beam dyeing.
5. Printing: Print-Thermofix.

19 DYEING OF COTTON MATERIAL WITH REACTIVE DYE

19.1 RECIPE FOR COLD BRAND REACTIVE DYES

19.2 RECIPE FOR HOT BRAND REACTIVE DYES

19.3 PROCEDURE
The given cotton material is weighted accurately. The dye bath is prepared by pasting the
dyestuff with water. The material is then steeped in the dye solution at 40o c for cold brand
reactive dye. sodium chloride is added in two portions and dyeing carried for 45minutes at 90o c
for hot brand reactive dyes. Then sodium hydroxide is added in two portions and dyed for
another 45 minutes. Then it is subjected for soap wash, cold wash with water and it is dried.

20 COTTON DYEING BY REACTIVE DYE - BATCH METHOD

20.1 PROCION-M
20.1.1 PROCION-M Recipe
Dyestuff → 3% (on product weight)
Salt → 60 gm/liter
Soda ash → 15 g/liter
Water → 10 times
Temperature → 40°C
Time → 1 hour

20.1.2 PROCION-M Dyeing Process

Cotton dyeing process by reactive dye batch method. First, the dyestuff is dissolved in a small
amount of water. The required amount of water is taken in the dye bath. Then add the dye
solution and salt to the dye bath and stir well. In this condition, the product is dyed for 20-30
minutes in the dyebath. Soda ash is then added to the dye bath and the product is re-dyed for 20
to 30 minutes. When the dyeing is finished, the product is first washed with cold water. Then
20% soap solution and 1% soda solution are heated for 30 minutes. Finally, the product is washed
and dried.

20.2 CIBACRON-E
20.2.1 CIBACRON-E Recipe
Dyestuff → 4% (on product weight)
Salt → 60 gm/liter
Soda ash → 20 g/liter
Water → 15 times
Temperature → 50°C – 90°C
Time → 1 – 1.5 hours

20.2.2 CIBACRON-E dyeing process

The paste is first made with cold water. Then a solution of dye is made by adding hot water. The
dye bath is heated to a temperature of 50°C. The product is then added to the dye bath and the
temperature is slowly raised to 60°C. In this condition, half of the salt is added and dyed for 10
minutes. Then add the remaining half of salt and dye for 30 minutes. Now the temperature is
raised to 90°C and dyeing is done for 40 to 60 minutes with the help of Soda Ash. The product is
then washed first with cold water and then with hot water. Then hot wash is done by heating in
soapy water (2 g/liter detergent). Finally, the cloth is washed with cold water and dried.

21 COTTON DYEING BY REACTIVE DYE - CONTINUOUS METHOD

21.1 PAD STEAM METHOD

21.1.1 Pad Steam Method Recipe
Light shade Medium Shade Dark Shade
Dyestuff 0.5-10 g/liter 10-20 g/liter Up to 30 g/liter
Soda Ash 5 g/liter 5-10 g/liter 10-20 g/liter
Salt 40-60 g/liter 60-80 g/liter 80 g/liter
Urea 150 g/liter
Sodium Alginate small amount small amount small amount

21.1.2 Pad Steam Method Dyeing Process

In this method, many clothes can be dyed together. In this case, two bowls are used. In the first
bowl, the wet cloth is padded with dye and urea at a temperature of 60-80°C. Urea helps the dye
to dissolve in water and penetrate the fabric. A small amount of sodium alginate is used in this
bowl as an anti-migrating agent. The cloth is then moved to the drawing chamber and taken to
the second bowl. The second bowl is padded at 60°C with soda ash or sodium hydroxide and salt.
The fabric is then steamed at 100°C – 102°C for 30 to 60 seconds. The cloth is then washed with
cold water and soaping. It is washed again with cold water and dried.

21.2 PAD THERMO FIXATION METHOD

21.2.1 Pad Thermo Fixation Method Recipe
Dyestuff → 2% (on product weight)
Soda Ash → 1% (on product weight)
Salt → 8% (on product weight)
Urea → 15% (on product weight)
Sodium alginate → a small amount

21.2.2 Pad Thermo Fixation Method Dyeing Process

In this method, the padding bath contains the solution of dyestuff, salt, urea, and sodium
alginate. The fabric is padded at room temperature in a padding bath. The cloth is then taken to
the drying unit for drying. After drying, the fabric is thermo fixed at 160°C for 5 minutes. The
fabric is then first washed with cold water, treated with soapy water, and then re-washed with
cold water. This method is quite useful for moderate reactive dye.

22 COTTON DYEING BY REACTIVE DYE - SEMI CONTINUOUS METHOD

22.1 PAD ROLL METHOD

22.1.1 Pad Roll Method Recipe
Dyestuff → 3% (on product weight)
Soda ash → 15 gm/liter
Salt → 60 gm/liter
Temperature → 20°C to 250C
Urea → 150 gm/liter
Sodium alginate → A small amount

22.1.2 Pad Roll Method Dyeing Process

The wet cloth is first padded in a bath containing dyestuff, alkali, urea, and wetting agent. At this
time the temperature is kept from 20°C to 25°C. The padded cloth is taken to a chamber in the
form of a roll. Four such rolls are made together and kept in the chamber at a temperature of
20°C and 100% humidity. While in the chamber, the rolls are rotated slowly. The batching time
may vary from 2 to 4 hours, depending on the dye’s reactivity. The cloth is then washed in cold
water and treated with a soap solution. Finally washed with cold water and taken for further
activities. This method is suitable for high reactivity dye.

22.2 PAD JIGGER METHOD

22.2.1 Pad Jigger Method Recipe
Dyestuff → 3% (on product weight)
Salt → 60 gm/liter
Soda ash → 15 gm/liter
Water → 15 times
Temperature → 40°C to 90°C
Time → 1 hour 30 minutes.

22.2.2 Pad Jigger Dyeing Process

First, the stock solution is made by measuring the quantity of dyestuff. The squared/bleached
cloth is then taken in a water bath. Then the dye solution is slowly added. After 10 minutes of
dyeing, add salt slowly and shake with the cloth. Soda ash is added 15-30 minutes after adding
salt. Then gradually increase the temperature from 40°C to 90°C and dye for 1 to 1.5 hours. It is
then washed thoroughly with cold water and treated with the soap solution and then re-washed.
Mention that light acid washing at the end of the dyeing process increases the brightness of the
shade.

23 AFTER TREATMENT OF REACTIVE DYES

When dyeing with reactive dyes, some of the dye fibers stick to the hydroxyl, which is usually
boiled for 30 minutes in a bath with 20% soap solution and 1% soda solution. However, this kind
of after-treatment gives good results in the case of precision dye but it is inconvenient in the case
of Remazol dye.
In that case, the product must be neutralized with acetic acid before soaping. The sticky dyes are
boiled only in a detergent solution. When boiled at high temperatures, the color spreads out
from the inside of the fiber. If sodium silicate is used as an alkali for fixing, there is no need to use
extra acetic acid. Because the fiber becomes very uneven.
The sequence of after treatments are mentioned below –
1. Rinsing for 10 minutes at normal temperature and hot wash at 800C for 10 min.
2. Neutralization by 1 gm/l CH3-COOH for 10 minutes.
3. Rinsing for 10 min at normal temp.
4. Soaping by 1 gm/l detergent for 20 minutes at 950C for medium and dark shade.
5. Hot wash at 800c for 10 minutes.
5. Rinsing for 10 minutes or cold wash.
6. Finishing if required.
7. Finally dry the fabric.

24 RIGHT FIRST TIME DYEING (RFT)

The concept of right-first-time (RFT) processing in exhaust dyeing became established in the late
1970s and early 1980s. Originally it was termed ‘no addition’ dyeing if the dyeing is found to be
on shade at the color assessment stage, or ‘blind dyeing’. If color assessment is carried out after
unloading the batch from the dyeing machine. Elimination of an inspection stage made a
significant saving of time and production. The technique is based on achieving a high percentage
of bulk dyeing that did not need color correction or reprocessing. The original benefits are seen
as cost savings and increased productivity in the coloration process. However, the introduction
of concepts such as just-in-time (JIT) production and quick response (QR) resulted in major
financial savings by minimizing time and chemical costs as well as increasing productivity.

24.1 NECESSITY OF RFT DYEING

1. No of fashion trends
2. Variety of fabrics
3. Color variation Increasing
4. Color fastness requirements
5. Environmental safety
Where as

1. Order size
2. Repeat orders Decreasing
3. Lead time
Alternatively, consumer requirements like Choice variation Fabric performance are also increasing Color
fastness Value for money.

The following factors create additional pressure on production cost Energy cost:
1. Water and effluent cost
2. Labor cost
3. Number of competitors

25 STRIPPING OF REACTIVE DYES

The reactive dye cannot be satisfactorily stripped from fibre due to the covalent bond between
dye molecule and fibre. Stripping becomes necessary when uneven dyeing occurs.
In dyeing textile fabric, it is often desirable to remove the color from the dyed fabric in order to
correct uneven dyeing or to redye the faulty fabric to a different color for reuse.
Stripping is the process, which is used to remove dye from dyed fabrics, and the process is either
designated "back stripping" or "destructive stripping". In back stripping, only the depth of shade
is changed while in destructive stripping, the dye is chemically altered. For example, dyes
containing an azo group (--N═N--) can be chemically reduced to an almost colorless amine
compound by using chemical reducing agents.

25.1 PARTIAL STRIPPING OF REACTIVE DYES

Partial stripping is obtained by treating the dyed fabric with dilute acetic acid or formic acid. Here
the temperature is raised to 70-100°C. It is continued until desired shade is obtained. The recipe
is as below:
• Glacial acetic acid : 5-10 parts or gm/L
• Water : 1000 parts
Or
• Formic acid : 2.5 to 10 parts
• Water : 1000 parts
• Temperature : 70 – 100°C
• Time : Until desired shade is obtained.

25.2 FULL STRIPPING OF REACTIVE DYES

For complete stripping, the goods are first treated with sodium hydrosulphite (hydrose) at boiling
temperature and then washed off. Then it is bleached with 1% sodium hypochlorite (NaOCl) at
room temperature. This is carried out for 30 minutes.
Other method includes, where goods are treated with sodium hydrosulphite (hydrose) and alkali
at boiling temperature. Then washed off and bleached with 1-2 gm/l bleaching agent (H2O2) at
100°C temperature. This is carried out for 30 min.
The recipe is as below:

• Sodium Hydrosulphite: 2-5 gm/L at boil

• Sodium Hypochlorite: 1% at room temperature
• Sodium Hydroxide: 5gm/L
• Time: 30 min

26 COTTON FABRIC PRINTING WITH REACTIVE DYE

The Procion dyestuff of the reactive group, invented by ICI is now widely used for printing, which
is fixed in the fiber through chemical linkage with the fiber. Printing can be done in different
shades by this Dye Staff. This Procion reactive dye can be divided into three ways. E.g.
1. Procion H dyes
2. Procion Supra dyes
3. Procion M dyes
❖ Procion H dyes:
This type of dye is slightly reactive. The durability of the printing paste made by this dye is
remarkable due to the low reactivity of this dye, which is why it is used by the steaming method.
❖ Procion Supra dyes:
The reactivity of this type of dye and the durability of the printing paste is comparable to that of
Procion H.
❖ Procion M dyes:
This dye is a more reactive type. Therefore, it is used in various techniques. This dye is useful in
both non-steaming and steaming methods. All these dye Chloratizine class paints, which belong
to the cold brand. Printing shades are available in a wide range of specific dyes of this Procion
class by mixing any proportion with any dye belonging to that class. Procion ‘M’ and Procion ‘H’
dye are not usually used interchangeably. However, it can be used in combination with Procion
H and Procion Supra.
The chemical linkage of fibers with Procion dye is usually organized in the presence of alkali and
under the influence of heat. The development process can be organized as follows:
1. Steaming process
2. Baking (dye heat) process
3. Flash-aging process
4. Air-hanging process
5. Wet development process
6. Pad (Alkali) batch process
No matter which of the above methods the printing paste is fixed on the cloth, there is a slight
difference in the material of the printing paste of each of these methods. Cotton fabrics can be
printed indirect style through various fixation methods by any class of dyes of Procion Reactive
Dye Staff.

27 WOOL FABRIC PRINTING WITH REACTIVE DYE

27.1 DIRECT STYLE PRINTING RECIPE

Procilanreactive Dye → 30%
Urea is dissolved → 50%
Water (boiling 80°C) → 400%
Myprogum AC → 500%
Perminal KB → 10%
Sodium bicarbonate → 10%
Total printing paste → 1000%

27.2 PRINTING PROCESS

Procilanreactive dye and urea are dissolved in boiling water. This solution is applied to the
MyProgum Thickener and then to the Perminal KB. After that Sodium bicarbonate is added just
before printing.
The chlorinated wool cloth is printed and dried by the mentioned printing paste. The cloth is then
steamed for 30 minutes. Clothes are washed in cold water while open. The cloth is then treated
for 3 minutes at a temperature of 80°C in a solution of 2% Lisapol ND mixture in 1000% water.
Afterward it is washed well in cold water and dried.

28 SOME QUESTIONS
1. Why are bifunctional reactive dyes preferable?
They have more than one identical functional group present in their structure. So, the degree of
fixation is higher because if one functional group gets hydrolyzed, others will remain
unhydrolyzed. Also, strict process control is not necessary.
2. Why reactive dyes were developed?
The main reason behind the discovery of reactive dye is that direct dyes have inferior wash
fastness properties with cotton. Also, the dyeing of cotton with sulfur and vat dyes includes a
very complicated process.
3. When did we discover the fiber reactive dyes?
During the 1900s, the idea of incorporating dyes with a covalent bond into the fiber was first
generated. In 1955, Stephen and Rattee (ICI, England) first dyed cotton with dichlorotriazine
reactive group-containing dye.
4. What is dye hydrolysis in reactive dyeing?
The most common problem of reactive dyeing is dye hydrolysis. In alkaline conditions, hydroxide
ion also reacts with the reactive group of the dye like the fiber, and hydrolyzed dye is generated.
The hydrolyzed dye can not react with fiber, and the efficiency of the fixation is decreased.
After dyeing, the hydrolyzed dye should be removed by washing. Otherwise, the wash fastness
will be reduced.
5. Are reactive dyes colorfast?
They show good to excellent fastness to different wet processing, although incomplete removal
of unreacted and hydrolyzed dye causes poor washing fastness. Lightfastness is moderate to
good. Fastness to peroxides and bleaching by chlorine is also moderate.
6. Can I use a fiber reactive dye for tie dye?
Of course, you can tie dye with reactive dyes. In fact, this is the type of dye molecules that are
marketed as Procion dyes for cellulosic fibers. Their use is not limited to solid colors only.
7. How Does Temperature Affect the Dyeing Process with Fiber Reactive Dyes?
Temperature impact on fiber reactive dyes is significant in the dyeing process. It mainly depends
on the type of reactive dye you are using.
Generally speaking, higher temperatures help facilitate the chemical reaction between the dye
and the fibers, resulting in a faster and more uniform color absorption. At the same time, it also
promotes a higher rate of hydrolysis.
Q.1. What are reactive dyes, and how do they work for textile printing?
A. Reactive dyes are a type of dye that forms a covalent bond with the fabric molecule, resulting
in a permanent bond. They work by reacting with the hydroxyl and amino groups on the fiber
molecules, creating a strong, permanent bond.
Q.2. What are the advantages of using reactive dyes for textile printing?
A. Reactive dyes have a high degree of color fastness, which means the colors do not fade easily
even after multiple washes. They can be used on a wide range of fibers, including cotton, wool,
silk, and rayon, and provide excellent penetration and brightness. Reactive dyes are also cost-
effective and produce vibrant and long-lasting colors.
Q.3. Are there any limitations of using reactive dyes for textile printing?
A. Reactive dyes require proper handling and a controlled environment, such as a stable pH and
temperature, to ensure optimal results. They are also more sensitive to impurities, such as salt
and alkaline residues, which can affect their performance. Moreover, reactive dyes are not
suitable for all types of fabrics, and the color range can be limited.
Question 1: Why Soaping is necessary after dyeing?
Answer: By soaping the extra dye molecule is removed from yarn or fabric surface that is not
permanent with fiber. Thus, soaping increases the levelness and stability of dyes in fabric and
wash, light, rubbing and perspiration fastness properties are improved. More than two times
soap wash are required in case of darker shade to increase the fastness properties of the colored
fabric. Only hot is enough to obtain the fastness properties of light shade.
Question 2: What happens if alkali is present in the dyebath before adding the dye or fixation alkali?
Answer:
1. Premature fixation before migration (unlevel dyeing)
2. Increase hydrolysis of dyestuff
3. Problem of shade reproducibility
4. Problem of RFT performance
5. Loss of time (sometimes need addition)
Question 3: Why stripping is necessary?
Answer: Stripping may be done in case of uneven dyeing of textile materials. It is also carried out if the
required shade (color depth) of textile material is not matched with standard or the shade is too much
darker than standard.