Challenges and changes in wool Dyeing

by
Prosenjit Pandit (2006TTF3054)
Introduction

Environmental demands on wet processing

Service the current and future needs of consumers

Innovation and high added value in higher quality
wool based products

All these product areas offer challenges to the wool
dyer to innovate and value to the final product
Why there is a change?


Fashion: Aesthetics, appearance, image or prestige

Consumer: Comfort, changing demands or lifestyle

Environmental: legal, ecological

Safety: legal, health or protection

Technical: innovation, new application
Disposal of waste chemicals

Health hazards

Level dyeing
Fastness to
Wash
Light
Chlorine
U/V
Perspiration
Maintaining uniform quality
Challenges faced by a wool dyer
Compatibility of dyes
Rate of uptake
Degrees of exhaustion of the dyes
PH
Surface levelness of fibre
Dyeing auxiliary
Dyeing time
Important criteria for wool dyeing
Development trends in wool dyeing
Dye class Consumption %
1960-1965 1990-1995
Chrome 45 20
1:2 metal complex 18 29
Acid milling 22 20
1:1 metal complex 8 7
Acid leveling 6 10
Reactive 1 5
Cuticle Structure of wool
Developments in pretreatment


Developments in dye


Developments in dyeing process

Developments

Low temperature plasma

Enzymes

Chitosan

Liposome

Chlorine treatment

Liquid ammonia

UV/Ozone treatment
Developments in Pretreatment
Low temperature plasma treatment
Plasma treatment is a degradative pretreatment
Modify chemically and topographically a surface without
altering the material bulk properties
Dye uptake increases
Limiting the fibre damage Controlled treatment
Oxidation of F-layer hydrocarbon chains and protein
cystine residues of the epicuticle and exocuticle
Cysteic acid residue formation conferring wettability and
reducing the number of cross linkages in the fiber surface.
Enzyme treatment
Wool shrink resistance improves

Better whiteness

Improved handle

Reducing wool fiber stiffness and prickle
SEM micrographs of wool treated 60 min with 1%, 4.5% and
8% of enzyme A (a, b and c respectively) and enzyme B (d,
e and f, respectively
Chitosan

Liposome

Chlorine treatment

Liquid ammonia

UV/Ozone treatment
Other Pretreatment Methods

Chrome dye

Acid dye

Metal complex dye

Reactive dye

Indigo dye

Natural dye
Developments in dyeing
Relationship between migration and fastness properties
for different dye classes.
Fastness
M
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a
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Reactive
Chrome
Supermilling
/1:2 MCD
Milling
Sandolan MF
1:1 MCD
Level dying
acid dye
Developments of chrome dyeing
Maximizing chrome dye exhaustion

Minimizing chrome addition

Maximizing chrome exhaustion in a fresh bath at PH 3.5-
3.8

Chemically reducing Cr (VI) to Cr (III) and complexing
with wool carboxyl groups

Rinsing to provide some dilution effect

By recycling using a standing bath technique for repeat
shades using the same dye liquor
Chrome dyeing Process
Chrome mordant dyeing

Metachrome or on chrome method

After Chrome
Chrome Mordant dyeing
Prechroming of wool is done
Application of the dye
Good coverage of wools of different dye
Permits simple shade matching
Requires two separate baths, and is consequently
expensive on time, energy and water
Causes significant fibre damage
Metachrome dyeing
Co-application of dye and chromium from a dyebath at
neutral pH (6.0-7.0)
Restricts uses in reasonable dyes at neutral affinity
Widely used in piece dyeing

Disadvantages
1. The limited number of suitable dyes
2. The inability to achieve very heavy shades
3. High residual levels of chromium
Afterchrome dyeing
Dyeing and then chroming processes

There is no restriction on shade

Gives better fastness properties

Disadvantage :Difficulty in shade matching
Practical aspects of chrome dyeing
Minimizing fibre damage
Low-temperature chrome dyeing
Chromium in dye house effluent
Dyebath exhaustion
Interfering chemicals
Specific processes to reduce residual chromium levels
Applied to wool from dye baths in acidic or neutral PH
(<pH 7.5) conditions

Has good affinity for wool

Fastness property depends on size of dye molecule

Acid Dye
Classification of acid dyes
Acid dyes are classified by their dyeing behavior and wet
fastness properties, rather than chemical composition.
Level-dyeing or equalizing acid dyes

Fast acid or acid milling acid dyes

Supermilling acid dyes
Level dyeing Acid dye

Monosulphonated and disulphonated dyes

Very low molecular weight(r.m.m 300-600)

Have very good levelling and migration properties

Wet fastness moderate

PH 2.5-3.5

Sulphate ions are necessary to assist migration and
levelness

Used for pale to medium-depth shades
Acid Milling dyes
Relative molecular mass about 600-900
The dyes cover a wide shade gamut
Superior wet fastness properties
Some degree of fastness to milling processes
The same dyeing method is used for all shades
They are applied at a pH(5-8) that minimizes fibre damage

They give high levels of dyebath exhaustion and shade
reproducibility
Supermilling Dye
These dyes have highest affinty toward wool fiber

Relative molecular mass is higher than 900

Wet fastness is maximum for this type of dye

Uneven dyeing can occur due to it high agglomeration
tendency
Metal complex Dye
Excellent all-round fastness properties

Pre-metallised acid dyes

Chromium is complexed with either one or two dye
molecules
1:1 METAL-COMPLEX DYES
Shows maximum exhaustion in the pH range 3 to 5

Dye will interact with the fibre by virtue of


a)ion-ion (electrostatic) forces operating between the
anionic dye and protonated amino (NH3) groups in the
fibre


b) Coordination of the chromium ion in the dye with
appropriate ligands (such as carboxyl or imino groups) in
the substrate
1:2 Metal complex dye
Two dye molecule is attached to one chromium

Good levelling and penetration of dye to the fiber

They can be dyed under neutral pH

They require less amount salt during application

Very good to excellent light fastness and very good
fastness to wet treatments in pale to medium depths
Reactive dye
Covalently bound to the various reactive groups in
protein fibers under neutral or mildly acidic conditions
have en found to be most suitable

Lanasol dyes
Drimalan F and Virofix dyes
Hostalan and Remazol dyes
Sumifix Supra dyes
Cibracron C
Calcobond
Cationic reactive dyes
Lanasol dyes
Chlorinated wool give high light and wet fastness properties
These dyes are normally applied at PH 4.5 to 6.5
Dyebath is set at 40C with an amphoteric leveling agent
Subsequently the temperature is raise to boil at rate of 12C
The dye bath is held at boil for 30 to 90 min
After dyeing alkaline pH (8.5) to promote further reaction of
the dye as well as desorbing of the hydrolyzed dye
The fixation of Lanasol dyes to wool is in the range of 86 to
96%
Indigo Dye
Indigo dye also can be applied on wool

Light fastness of indigo dye on wool(7-9) is better than
cotton(4-6)

Indigo is adsorbed more strongly by wool

It is now getting popular in the worsted denim sector
Natural dye
Natural dye was used from the very fast stage of dyeing

It was going to omit from the market but it is coming back
again

Eco-friendly

Metal salt or tannin is used as mordant to apply natural dye

Problem is very low all round fastness.
Dyeing in a reverse micellar system
Acid dye solubilized in the interior of reverse micelle was
satisfactorily adsorbed on wool

Reactive dyes also have a high ability to adsorb on fiber in a
reverse micellar system


Low dyeing property of wool in a reverse micellar system may
be attributable to the characteristic structure of the wool fiber
Dyeability of acid dye (C.I. Acid Blue 83) on wool in a Reverse Micellar
system.
Supercritical processing
Mordant dyes dissolved in supercritical carbon dioxide with
chelating ligand properties

Carbon dioxide has been the most widely applied
supercritical fluid

The chelation reaction requires that the metal be in its ionic
form

Optimum conditions for dyeing and the dyeing period is
controlled by the solubility of the dyestuff in supercritical
carbon dioxide
Ultrasonic assisted dyeing
Cavitations in a liquid medium that is the growth and
explosive collapse of microscopic bubbles
Sudden and explosive collapse of these bubbles can
generate hot spots shock waves
This severe shear force capable of breaking chemical
bonds
Ultrasonic increases the dye-uptake of wool fibres
Lac dye, the enhanced effect was about 41% and 47%
Saving the processing time and energy
Better environmental impact and efficient dye bath reuse
Dyeing with disperse dye
The substantivity of disperse dyes towards the fibre could
be increased by increasing the hydrophobicity of wool

Wool chemically modified with various hydrophobic
compounds

Such treatment improve both the wash and light fastness

In the presence of a radical initiator covalent dye fibre
bond is formed
Developments in dyeing style
Top dyeing: Lonclose machine for large bump tops,
Obem Big Form Vigoreux Printing

Loose stock: Wronz Soft flow machine, Continuous
dyeing,

Yarn dyeing: Hank dyeing, HT-HP dyeing i.e. Horizontal
and vertical

Piece: Jigger, Winch, CDR, Jet dyeing machine.

Garment dyeing: Finox side-paddle machine, Milnor
rotary drum machines
Dyehouse and chemical control
The central computer is used for dyeware and chemical
control with the following functions:

Recipe storage

Automatic recipe card production

Stock control from recipe cards

Controlled/recorded dye and chemical weighing with stock
update

Automatic dispensing of liquid chemicals or dyes.
Colour measurement
Recipe calculation for laboratory and production dyeing to give
minimum dye cost and metamerism

Recipe correction for laboratory and production dyeings

Recipe adjustment for multiple batch dyeing of slubbing or loose
fibre
Coloured fibre blend matching

Shade passing - shade sorting

Fastness rating

Dye strength measurement

Shade library.
Conclusion
Changes in the wool dyeing is going for challenges
imposed by market as well as environmental demand

Some dyes are going to obsolete and some new are
developing

Computer color matching and online monitoring
system is getting incorporated in the dyehouse to
control quality and productivity
Thank You for Your
attention