GREEN UNIVERSITY OF BANGLADESH

Department of Textile Engineering

Assignment

Course Code:-TE-305.
Course Title:- Textile Coloration ll.
Assignment Type:-Midterm Assignment.

Submitted to:- Submitted by:-

Name:Md Mahabubur Rahman Name:-Md Sagor Hasan
Designation:Lecturer ID No:-191014037
Department:Textile Eng: Department:Textile Eng:
 Answer to the question no:01
Question:- Explain the reason of cotton dyeing with Reactive
dyes is more suitable in the textile industry.
Answer:-
Reactive dye is a class of dye that makes a covalent bond with the
fiber and becomes an integral part of the fiber. These are usually
used to dye cellulosic fibers such as cotton, rayon, or flax, but
polyamide, wool, silk, and acetate fibers can also be dyed using
reactive dyes.
Reactive dyes are so-called because this is the only type of dye
that has a reactive group. This group reacts chemically with the
fiber polymer molecules to form covalent bonds. This covalent
bond is formed between the reactive group and terminal –OH
group of cellulosic fibers and terminal –NH 2 group of polyamide
and wool fiber.
if we assume the general structure of reactive dye is S–F–T–X,
then this can be described as:
S–F–T–X + fibre = S–F–T–X–fibre
Where,
 S = Solubilising groups (such as SO3Na or COONa or
combination of both)
 F = Chromophoric group usually an azo, metal-complex azo,
anthraquinone, etc.
 T = Bridging group which attaches the reactive system X to
the chromogen F; Usually, –NH, –O–, –NHCO–, –OCH3–, –
SO3–, etc.
 X = Reactive system or group, which reacts chemically with
the functional group of the fibre.
 Here’s an example of reactive dye with its various parts:

Various Parts of a Reactive Dye

Some Trade Names of Reactive Dyes

Brand name Manufacturer Country

Procion I.C.I. UK

Novacron Huntsman Switzerland

Remazol Hoecht Germany

Levafix Bayer Germany

Reactone Geigy Switzerland

Primazin BASF Germany

Drimarine Sandoz Switzerland

Classification of Reactive Dyes

1.On the basis of reactive group
 Halogen
  Triazine group:procion,cibacron
 pyrimidine group:reactone
 Quinoxaline group:Levafix
Activated vinyl compound:
 Vinyl sulphone:remazol
 Vinyl acrylamide: primazine
 Vinyl sulphonamide: levafix

2.On the basis of reactivity

 Lower reactive dye: here pH is maintained 12-12.5
using NaOH in bath
 Medium reactive dye: pH is maintained 11-12 by
Na2CO3
 Higher reactive dye: pH is maintained 10-11 using
NaHCO3
3.On the basis of dyeing temperature
 Cold Brand Reactive Dyes
These types of dyes contain reactive groups of high reactivity. So
dyeing can be done in lower temperature i.e. 32-60°C. For
example: PROCION M, LIVAFIX E
 Medium Brand Reactive Dyes
This type of dyes contains reactive groups of moderate reactivity.
So dyeing is done at higher temperatures than that of cold brand
dyes i.e. in between 60-71°C temperatures. For example,
Remazol, Livafix are medium brand dyes.
 Hot Brand Reactive Dyes
This type of dye contains reactive groups of least reactivity. So
high temperature is required for dyeing i.e. 72-93 °C temperature
 is required for dyeing. For example PROCION H, CIBACRON are
hot brand dyes.

Recent Classification Of Reactive Dyes

Type Reactivity Condition Temperature Reactive Group

Appreciable
Low reactivity in substantivity, careful Monochloro Triazine,
alkaline addition of salt is Monofloro Triazine,
Salt Controllable conditions required. 80°C temperature. Trichloro Pyrimidine.

Moderate Dichloro Triazine,

substantivity, careful Diflorochloro
control of the addition Applicable at low Pyrimidine, Vinyl
Alkali controllable High reactivity of alkali is required. temperature. Sulphone.

Temperature Can be applied in Applicable in high

controllable – neutral conditions temperatures. NT.

Dyeing Mechanism of Reactive Dyes

The dyeing of material with reactive dye takes place in 3 stages –

 Exhaustion of dye in presence of electrolyte or dye absorption

 Fixation under the influence of alkali
 Wash-off of the unfixed dye from material surface
Absorption of Reactive Dyes
When fibre is immersed in dye liquor, an electrolyte is added
to assist the exhaustion of dye. Here NaCl is used as the
electrolyte. This electrolyte neutralizes cotton and helps
absorption. So when the textile material is introduces to dye
liquor the dye is exhausted on to the fibre.
Reactive dyes are so popular due to the following reasons:
ü Good washing fastness (Rating 4 – 5).
ü Very good light fastness (Rating 6).
ü Lower cost.
These dyes react with fiber forming a direct chemical linkage
which is not easily broken. Their low cost, ease of
application, bright shades produced by them coupled with
good wash fastness make them very popular with piece
good dyers.
Fixation of Reactive Dyes
Fixation of dye means the reaction of reactive group of dye
with terminal –OH or –NH2 group of fibre and thus forming
strong covalent bond with the fibre .
This is an important phase, which is controlled by
maintaining proper pH by adding alkali.The alkali used for
creates proper pH in dye bath and work as the dye-fixing
agent. The reactions that take place in this stage are shown
below:
 Nucleophilic substitution (a) and addition reactions (b) of reactive
dyes with cellulose.

Types of Fixation Reaction

There are mainly two types of reactions that occur. These are –
Neucleofilic Substitution Reaction
Cell–OH + HO– ⇒ Cell–O– + H2O
Cell–O–+ Dye–Cl ⇒ Cell–O–Dye + Cl–
 
Neucleofilic Addition Reaction
            Cell–O–+ Dye–SO2–CH=CH2 ⇒ Dye–SO2–CH=CH2–O–Cell

Wash-off of Reactive Dyes

As the dyeing is completed, a good wash must be applied to
the material to remove extra and unfixed dyes from material
surface. This is necessary for level dyeing and good wash-
 fastness. It is done by a series of hot wash, cold wash and
soap solution wash.

Properties of Reactive Dyes

 All types of shades are available from these dyes.
 Reactive dyes are found in powder, liquid, and print-paste
form.
 Reactive dyes are soluble in water.
 They have very good light fastness with a rating of 6. The
dyes have very stable electron arrangements and can protect
the degrading effect of ultra-violet rays.
 Textile materials dyed with reactive dyes have very good
wash fastness with a rating of 4-5 due to strong covalent bonds
formed between fibre polymer and reactive group of dye.
 Reactive dye gives brighter shades and has moderate
rubbing fastness.
 Reactive dyes have good perspiration fastness with rating 4-
5.

Factors to Be Considered During Reactive

Dyeing
 pH – Strong alkaline pH is required ranging from 10.5-11.2.
 Temperature – Dyeing temperature depends on the brand of
dye used.
 Concentration of electrolyte – The depth of shade is the
determining factor of electrolyte concentration.
 Time – Ranges from 60-90 minutes.
 Liquor ratio – Higher liquor ratio gives better efficiency.

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.

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. The amount of acid used is as below:
 Glacial acetic acid: 5-10 parts
 With water: 1000 parts
Or
 Formic acid: 2.5 to 10 parts
 With water: 1000 parts
 Temperature: 70 – 100°C
 Time: until desired shade is obtained.

Advantages of Reactive Dyeing

 Brilliant, bright colours
 Permanency of the colour
 Covalent fixation – high Wash Fastness (WF)
 Various temperatures, including low energy (cold dyeing)
Disadvantages of Reactive Dyeing
 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.
Precautions for Reactive Dyeing
  Hot water should not be used for high reactive dyes because
there will be a possibility of hydrolysis.
 Prepared dye solution can not be stored for later use also
because of dye hydrolysis.
 For making print paste, low reactive dyes are used.
 It is dangerous if there is the inhalation of the dust of reactive
dyes, so a protective mask is required.
 A limited storage period is applicable to most of the reactive
dye.

Answer to the question no:-02

Why heat setting is an important factor for polyester
fabric dyeing with disperse dyes?

Disperse Dyes
The development of disperse dyes was carried-out to permit
the dyeing of hydrophobic thermoplastic fibers (ex. acetate,
triacetate, nylon, polyester, acrylic) and other synthetics.
These dyes are mostly substituted azo, anthraquinone, or
diphenylamine compounds that are sparingly water-soluble and
non-ionic.
Above, both colors were found to be applicable to polyester.
However, as polyester has a very compact structure, the dyes
being inferior to them. So, it was necessary to modify the original
cellulose acetate dyes from their fastness and dyeing character
point of view.
In one of such developments, the application of the insoluble dyes
in the form of micro-fine dispersion called as disperse dyes were
brought into commercial practice.

Classification of Disperse Dyes

Disperse dye can be categorized based on:

 Field of Application
1. ‘No suffix’ dye: It is not suitable for polyester, but ideal
for acetate and nylon.
2. Group A dye: It has poor sublimation fastness (~Grade
2), suitable for acetate and nylon, but may be used for
polyester.
3. Group B dye: It shows moderate sublimation fastness
(~Grade 2–3), is suitable for acetate and nylon. Well-leveled
shades on polyester, coverage on ‘configurational barre’ is
excellent, and so is invariably applied on textured polyester.
4. Group C dye: It has good sublimation fastness (~Grade
3–4), is suitable for all methods to dye polyester, e.g., carrier,
HTHP, thermosol, and other processes, where maximum
sublimation fastness is not required.
5. Group D dye: It has maximum sublimation fastness
(~Grade 5). Exclusively for dyeing of polyester in HTHP or
thermosol technique but not in carrier method.

 Chemical Nature:
1. Azo disperse dyes
2. Anthraquinone disperse dyes
3. Other disperse dye classes
 Nitroarylamino disperse dyes
 Coumarin disperse dyes
 Methine disperse dyes
 Naphthostyryl disperse dyes
 Quinophthalone disperse dyes
 Formazan disperse dyes
 Benzodifuranone disperse dyes
  Different Properties (Polyester Dyeing)
Classification Molecular Weight Polarity Dyeing Rate Sublimation Fastness

Low energy Low Low High Low

Medium energy Moderate Moderate Moderate Moderate

High energy High High Low High

Properties of Disperse Dyes

1. Disperse dyes are low molecular weight substances,
mostly derived from azo, anthraquinone, and diphenylamine.
2. They are crystalline materials of a high melting point
(>150ºC).
3. They are marketed in both powder and liquid forms.
4. These dyes are electrically neutral, thus non-ionic in
nature. No strong solubilizing groups like sulphonic or carboxyl
groups are present. However, weak solubilizing groups like
aromatic or aliphatic –NH2, −NHR, and –OH groups may be
present and do not have an affinity for any fiber.
5. They have particularly low water solubility (sparingly
soluble).
6. They must be dispersed in water using a dispersing
agent. Otherwise, a carrier must be used.
7. These dyes have a relatively high saturation level in the
fiber (30-200 mg/g of fiber).
8. Due to the absence of ionizable groups, these dyes
tend to sublime without decomposition. Consequently, the
color of disperse-dyed fabric may fade while ironing.
 9. Certain disperse dyes tend to fade when stored in an
atmosphere having fumes from gas heaters.
10. The dyes having identical chromophores (indicated by
C.I. number) produced by different manufacturers. They may
not give identical shades on dyeing. The shade produced
depends on several factors like shape, size, and volume of the
dye crystals, colored impurities or isomers, type and amounts
of dispersing agents, and products added for standardization.

Fastness properties of Disperse Dyes

Both the light fastness and the fastness to washing of these dyes
on synthetic and acetate fiber is usually moderate to good.

Fastness Property Comment

Washing Good

Light Good

Crocking/Rubbing Moderate to good

Gas fume fading Moderate

Chemical Constitutions of Disperse Dyes

1. Most of these dyes have low molecular weight. They
are mainly mono azo and anthraquinone derivatives.
2. The reason behind the huge number of azo disperse
dyes is that the number of possible substitution patterns in
different diazonium ion and coupling components are high.
3. Anthraquinone disperse dyes are usually 1-hydroxy or
1-amino derivatives having bright colors ranging from red to
blue.
Polyester Dyeing with Disperse Dyes
 Polyester is undyeable below 70-80°C and the rate of
diffusion of disperse dyes into polyester below 100°C  is so low.
 HTHP Method: 130°C temperature is required for its
dyeing. For dyeing using the HTHP method, special
equipment is needed, which can withstand such
conditions.
 Carrier Method: The fiber can be dyed in a boiling
dyebath at atmospheric pressure in the presence of the
carrier. The main function of the carrier is to reduce the Tg
of the fiber.
As these dyes are insoluble or only slightly
soluble in water, they are applied from an aqueous dispersion
in the presence of a dispersing agent.
 They require slight acidity for their exhaustion into the fiber.
The acidity is achieved by adding acetic acid (pH of 4.0–4.5).

Mechanism
The mechanism of the disperse dyeing of a hydrophobic fiber
such as PES can be considered to comprise five sequential
stages. They are:
1. Dissolution of dye molecules from the surface of
dispersed dye particles and the establishment of a
monomolecular state in the aqueous dyebath.
2. Convective diffusion of the dissolved dye molecules
through the bulk dyebath to the fiber structure.
3. Diffusion of the dye molecules through the diffusional
boundary layer present at the fiber surface.
4. Adsorption of the dye molecules onto the surface of the
substrate.
5. Diffusion of the dye molecules within the fiber interior.
Heat setting of polyester:
Heat-setting is a heat treatment by which shape retention,
crease resistance, resilience and elasticity are imparted to the
fibres. ... This is process for the stabilisation of synthetic fibres so
they do not shrink on heating. Polyester shrinks -7% in boiling
water and 20% at 220 degree C.
Two common mordants are salt and vinegar.
Alternatively, dyes can be set with heat. This is accomplished by
using a hot dryer or iron to create a
damp heat that sets the dye on the fabric. It's important to check
the dye manufacturer's recommendations carefully before
proceeding with a dye project.
Disperse dyes became fuse or sublimate instead of
decomposing when heated to the temperature of 150 - 230 deg
C, that is, they become easily gasified from the solid state in the
heated dry air.
Importance of Heat Setting:
Heat-setting affects the dye-ability of the fiber. Usually it
decreases its dye-ability, and therefore when performed before
dyeing it is extremely important to apply
the heat- setting uniformly.

The End