Dyeing of Polyester

Introduction to Polyester
• Polyester is nonionic, hydrophobic and thermoplastic in
nature.

• Its highly compact structure permits efficient dyeing only at

high temperature with disperse dyes, preferably in closed
machines.

• Fibre structure is too compact and hinders chemicals to enter

inside below its glass transition temperature (Tg ~ 85°C)

• For polyester disperse dye the activation energy required is

~30 kcal.
 Contd.
• Fibre structure is too compact and hinders chemicals to enter
inside below its glass transition temperature (Tg ~ 85°C).

• Beyond Tg, structure slowly opens up with corresponding

increase in pore size at the surface and interior extent of
opening is directly proportional to increase in temperature.

• For dyeing, required opening in structure is obtained just

above 120°C for efficient diffusion of dye, although surface
deposition is allowed beyond 104°C.
Below glass At glass transition (Tg) At Melting (Tm)
transition (Tg)
What dyes can be used to dye Polyester?
• Polyester can be dyed only by using disperse
dyes.

• Why?
 Disperse dyes
• Disperse dyes are water insoluble non-ionic dyes and are used
to dye do not possess affinity for any fibre and are mainly
used for dyeing of non-ionic fibres, e.g., polyester, cellulose
acetate etc.

• The dye has been assigned such a name because of the use of
dispersing agent to retain dyes in fine dispersion.

• Dye particles size ranges from 0.5–2.0 micron, generally

contain –NH2, substituted –NH2 or –OH groups in structure
and are attached with fibre through H-bond and Van der
Waals force.
Chemical structure of disperse dyes
Almost 60% of all disperse dyes belong to azoic class,
out of which only monazo dyes contribute for about
50%, anthraquinoids around 25% while rest from other
miscellaneous classes.
 Classification of disperse dyes
• ‘No suffix’ dye: Not suitable for PET, but suitable for acetate
and nylon.

• Group A dye: Dyes have poor sublimation fastness (~ grade

2). Suitable for acetate and nylon and may be used for
polyester.

• Group B dye: Shows moderate sublimation fastness (~ grade

2–3). Suitable for acetate and nylon. Well-levelled shades on
polyester.

• Group C dye: Dyes have good sublimation fastness (~ grade

3–4). Suitable for all methods to dye PET, e.g., where
maximum sublimation fastness is not required.
• Group D dye: Dyes have maximum sublimation fastness (~
grade 5).

• Exclusively for dyeing of polyester in HTHP or thermosol

technique but not in carrier method; few dyes produce wash
fast shades on nylon.
 Dispersing agents
• Dispersing agents belong to mainly formaldehyde
condensates of either of naphthalene sulphonic acid, cresol,
1-naphthol 6-sulphonic acids, fatty alcohol ethylene oxide
condensate, alkyl aryl sulphonates or lignin sulphonates.

• The condensate of naphthalene sulphonic acid is the most

popular one.
 Mechanism of dispersing agent

• Dispersing agent imposes negative charge on dye to improve its

aqueous solubility and inhibits formation of dye cluster through
repulsion among negatively charged dye molecules and retains dye
in consistent dispersion throughout dyeing by enclosing single dye
particle with a protective film.
 Dyeing mechanism
✓ Deposition of dye on surface at lower temperature,

✓ Diffusion at the surface layers with increase in temperature &

✓ Diffusion at the interior at higher temperature the rate of diffusion

at the interior is the rate determining step in dyeing.

• Disperse dyeing of Polyester follows a solid–solid interaction

where a solid dye is solubilised in another solid fibre phase.

• Once distribution of dye is over, the bath is cooled down to collapse

fibre structure in which dye remains attached with fibre through H-
bonds and Van der Waals forces.

• In spite of weaker nature of these bonds, wash fastness remains

excellent as dye cannot comes out from compact fibre structure.
 Methods of dyeing polyester
There are four methods for dyeing polyester, viz.

(i) Dyeing at boil without carrier,

(ii) Dyeing at boil with carrier,
(iii) HTHP dyeing &
(iv) Thermosol dyeing.

• The first three methods are batch methods whereas the

thermosol method is a continuous one.
 Dyeing at boil without carrier
Recipe
Dye
Dispersing agent
Acetic acid (pH ~ 5.5–6.5)
Temperature : Boil

• Dyeing is started at 50–60°C, raised slowly to boil and is

carried out at this temperature for 2–3 hours followed by
soaping and washing.
 Demerits
• This method is used only for pale shades fibre opening is too
little at boil, necessitating use of only low molecular weight
disperse dyes.

• Dyes do not penetrate due to very limited opening causing

poor wash and sublimation fastness ratings domestic pressing
causes partial sublimation of dye too.

• This method has least commercial importance except for very

light shades on P/C or like blends.
 Dyeing at boil with carrier
• Carrier brings down Tg of polyester and swells up fibre
structure for better diffusion of dye at boil.

• Chemically carrier belong to hydrocarbons or substituted

hydrocarbons, phenols, amides, alcohols etc. Few popular
carriers are monochloro-o-phenylphenol, o-phenyl phenol,
diphenyl, monomethylnaphthalene, halogenated benzenes,
methyl salicylate, butyl benzoate etc., and are highly toxic.

• Dyeing method is same as the previous one except the

addition of carrier at 80°C.

• After dyeing, dyebath is discharged and dyeings are washed

with anionic or non-ionic detergent along with Na2CO3 (2–3
g/l each) to remove last trace of carrier.
Figure 2. Disperse dye uptake on polyester in presence and absence of carrier
• This method is restricted to production of light shades with
negative impact of carrier, e.g.,

• Irritation on skin,

• Poor light fastness and

• Spotting due to volatile nature of carrier.

High temperature high pressure dyeing
• HTHP dyeing is the most popular commercial batch method of
dyeing polyester to produce levelled shades.

• The process is based on opening of fibre structure at higher

temperature, includes no carrier and generates lesser waste
water load.

• Disperse dyes show feeble water solubility beyond 90°C; a

part of disperse dye goes into solution with simultaneous
affinity for polyester, the higher the temperature the better
the solubility and the higher the affinity due to more solubility
of dye as well as opening of fibre.
 HTHP dyeing method
• Dyebath is prepared with acetic acid (pH ~ 5.5–6.5) and
dispersing agent.

• Temperature is raised to 60°C, dye is added and temperature

is again raised to 90°C beyond which rise in temperature is
restricted to 1–1.5°C/min up to 117°C, and beyond that
temperature is raised quickly to 130 ± 2°C at corresponding
steam pressure around 3–3.5 kg/cm2 and continued for 0.5–2
hours depending on the depth of shade.

• Dyeing follows reduction cleaning of dyed PET with NaOH and

Na2S2O4 (3 g/l each) at 50–60°C for 15–20.
• Equilibrium is only reached when the subsidiary equilibria are
achieved through a balance in all the dyeing steps, viz.

(i) dye dispersed in bath ↔ dye dissolved in bath

(ii) dye dissolved in bath ↔ dye adsorbed on fibre

(iii) dye adsorbed on fibre ↔ dye diffused in situ fibre

• HTHP dyeing is a unique method as all types of well levelled shades
with superior fastness can be produced on polyester and its blends.

• Dyeings are generally performed either in jet dyeing machine in

rope form or in open width in beam dyeing machines.

• Levelling of shade crucially varies with control over temperature. Up

to 100°C, as high as 10% of the bath is exhausted, 80% exhaustion
occurs during 100–120°C and the rest 10% between 120–130°C.

• Neither the initial nor the final absorption stages affect levelling
and so such control over heating of bath is necessary, but an
efficient control is needed during heating in the range of 100–120°C
 Thermosol dyeing
• In this process, dye is forced to get solubilised in solid fibre
phase through partial loosening of intermolecular bonds
under heat treatment when the internal structure of the fibre
opens up to allow dye molecules to diffuse at the interior.

• The process is not viable for 100% PET due to feeble pick up
of liquor during padding as the fibre is highly hydrophobic in
nature.

• Thermosol of P/C blends, where cotton picks up dye liquor

from bath and transfer it to the PET phase at high
temperature during curing process is unique for continuous
dyeing
 Dyeing procedure
Pretreated P/C fabric

Padding 80% Expression

Dye + Acid + Disp. agent

Infrared drying at 90 to 100⁰C

Curing at 180 – 190⁰C for 45 – 60s

The coating of dye dispersion on fabric is very sensitive to touch and so the padded material
be instantly passed through drying zone without any contact with guide rolls or other
accessories.
• Due to hydrophobic nature of polyester, dye concentration is
kept on higher side.

• Liquid disperse dyes provide excellent result due to high rate

of dispersion and diffusion.

• Dyes from B and C classes possessing moderate sublimation

and wash fastness properties may be selected for levelled
shades.

• Dyes form D class produce excellent fast shades but are not
recommended on grounds of having higher sublimation
temperature and excess of dye is required to produce desired
depth due to poor diffusion coefficient.
 Fastness of dyeings
• Disperse dyes generally exhibit overall good fastness
properties.

• Light fastness depends on stability of dye structure with

number of double bonds, substituent groups and their
location in dye structure – lesser double bonds imparts better
stability, the better the light fastness.

Presence of –NH2 groups in anthraquinone structure lowers light fastness through

oxidation to –NO2 on exposure to strong light, known as gas fading.
• Sublimation fastness remains directly proportional to
molecular weight of dye, polarity and amount of dye on fibre
surface – better the diffusion the better the fastness.
End of the lecture