Dyeing and

Finishing
technology on
Polyester fibre and
its blends
Wirote Sarakarnkosol

Outline

Preparation of polyester fiber

Disperse dyes
Dyeing and auxiliary for polyester fiber
Finishing on polyester
Polyester blends dyeing

Polyester
Most popular in synthetic fibres
Hydrophobic
High strength and good mechanical
property
Rapid growth in fibre blends
Can be modified to variation of finishing

Variation in market share of

fibres
World share (%)
Fiber

1980

1990

2000 (est)

2010 (est)

Cotton

47

47

40

31

Wool

5.4

4.2

2.6

2.0

Regenerated cellulose
(staple and filament)

11.5

8.1

4.8

4.1

Polyester
(staple and filament)

18.0

22.0

34.0

39.5

Nylon
(staple and filament)

9.9

9.6

7.3

6.6

Polypropylene
(staple and filament)

1.5

3.0

6.0

12.0

Acrylic

6.8

5.8

5.0

4.6

total

100

100

100

100

Preparation of polyester fibres

for dyeing

Scouring
Bleaching
Weight reduction
Heat setting

Sizing agents for different substrates

Scouring :
PES contain larger quantities of
processing aid and oily dirt
General recipe for washing
1 g/l
non-ionic detergent
2 g/l
soda ash
1 g/l
sequestering agent
95oC on a tensionless open-width washing range

Not only remove the size and processing

aid : Also developing bulk for texture yarn
Sometime calls RELAXATION

Bleaching :
Rarely necessary for 100% PES
NaClO2 is only effective
Higher whiteness can be achieved with
nonionic FWA
Condition for PES/CEL and PES/WO will
depend on the blends fiber

AOX values of NaClO2 on

various synthetic fiber
Sizes and lubricants are often prime sources of higher
AOX values rather than the substrate itself

Effect of surfactant addition on AOX values after chlorite bleaching of

synthetic fibres

Alkaline pretreatment for weight

reduction
NaOH has been used to achieved a
weight reduction of 10-15%
Result in improve handle and hydrophilicity
Degree of weight reduction depend on
concentration of NaOH, Temperature and
treatment time.
Cationic accelerating agent can use as the
catalyst for weight reduction

Heat setting :
Serve to stabilise polyester fabric and
retain the shape of fabric
Condition are governed by the processing
history as guide condition
Woven and knitted good of texture filament :
170-190oC
Polyester filament : 185-220oC
PES/CEL blends : 190-210oC

Heat setting :
Should avoid problems with shade
variations during dyeing
Pre-setting has a negative on dye yields.
Post-setting generally adversely fastness
and colour change particular for ring
dyeing or incompatible dyestuffs.
Sublimation fastness of selected dyes
should be concerned.

Disperse dyes : Chemistry

Hydrophobic and nonionised
Can be classified as

Azo dyes
Anthraquinone dyes
Styryl (Methine) dyes
Nitrodiphenylamine dyes
Heterocyclic ring structure dyes
Benzodifuranone dyes
Thiophene dyes
Etc. but not phthalocyanine

Chemical structure present in

colorant of variation of hues
Hue

Typically chemical structure

Brillant Yellow Methine ; Coumarin ; Pyridone

Yellow

Nitrodiphenylamine ; Heterocyclic ; Azo with pyridone coupler

Orange

Azo

Red

Azo; Anthraquinone ; Benzodifuranone

Pink

Anthraquinone ; Benzodifuranone

Violet

Azo; Anthraquinone

Blue

Azo; Anthraquinone ; Thiophene

Black

Mix of azo

Classification of Disperse dyes

with dyeing property
Class A : Low MW , High migration
Low sublimation fastness for acetate fibre

Class B : Slightly Higher MW, Lower migration

Suitable for carrier dyeing on PES

Class C : Higher MW, Lower migration than

Class B
Suitable for HT dyeing on PES

Class D : Highest MW, Lowest migration

Suitable for Pad-Thermosol on PES

Disperse dye :
Commercial name

Dianix
Terasil
Foron
Sumikaron

(Dystar)
(Huntmann)
(Clariant)
(Sumitomo)

Alkaline clearable disperse dyes

Must control dyeing pH below 5 (or some pH 4)
Avoidance of a reduction clear with dithionite as
conventional disperse dyes.
Minimal cross-staining of the cellulosic fibre
Minimal processing time because the alkaline
fixation for reactive dyes clears the disperse dye
stain.
Good washing fastness performance after heat
setting during finishing.

Mechanism of alkali clearing

Undergoes hydrolyse
under relatively mild
alkaline conditions to give
a water-soluble structure
Lability of the thienyl ring
system are easy to alkali
clearing than normal

Undergoes hydrolyse
under relatively mild
alkaline conditions to give
a pigment and cant stain
on fabric

Essencial auxiliary for disperse

dyeing

Dispersing agents
pH control and sequestering agents
Electrolytes
Levelling agents
Carriers
Antireduction

Dispersing agent
Disperse dyes being an
overall tendency of fine
particles to formation of
larger particles
Beam and package
demands on initial
dispersion and
subsequent stability
under adverse conditions
Jig dyeing with a high
concentration of dye in a
very short liquor (as for
navy blues and blacks)
can also be the source of
dispersion stability
problems.

Effect of temperature changes on the

particle size distribution in a dyebath
containing 0.6% CI Disperse Orange 13

Typical conventional dispersing agent

condensation product of naphthalene-2sulphonic acid and formaldehyde

lignosulphonate

condensation products of phenols with

formaldehyde and sodium sulphite

condensation products of p-cresol and 2-naphthol-6sulphonic acid with formaldehyde and sodium bisulphite

Dependence of dispersion thermal

stability on dispersing agent structure

Effect on reduction of sensitive

dyes
Naphthalene-sulphonate
condensation types
Higher promote
reduction
of sensitive dyes

Lignosulphonate
Presence in lignin of catechol residues
and other easily oxidised functional groups

pH control:
Many disperse dyes give good results over an
extensive pH range (pH 29)
Some will only give satisfactory results over a
narrower acidic range (pH 26)
Few require careful control (pH 4 - 5.5)
Practically all dyes
provide good results
at pH 5

pH control:
Normality
Material

pH value of some common acid in distilled water.

2N

1N

0.1 N

xN

0.01 N

0.001 N

Hydrochloric acid

g/l

36.5

3.65

1 g/l

0.37

0.037

HCl

pH

0.11

1.08

1.61

2.00

3.00

Sulphuric acid

g/l

49.0

4.9

1 g/l

0.49

0.049

H2SO4

pH

0.24

1.17

1.79

2.05

3.00

Formic acid

g/l

92.0

46.0

4.60

1 g/l

0.46

0.046

HCOOH

pH

1.61

1.79

2.32

2.76

2.85

3.42

Lactic acid

g/l

180.0

90.0

9.00

1 g/l

0.90

0.090

C3H6O3

pH

1.78

1.97

2.43

2.94

2.95

3.50

Acetic acid

g/l

120.0

60.0

6.00

1 g/l

0.60

0.060

CH3COOH

pH

2.18

2.40

2.87

3.27

3.37

3.89

Alkaline dyeing of polyester

Mitsubishi kasei (Dystar japan) announce
in 1993
Over 30% oligomer reduction
Cleaner machinery
Time saving (270 min to 190 min)
Reduced BOD/COD in effluent
Water and energy saving (2/3 cost with
normal condition)

Essential primary requirement

for alkaline dyeing
Selecting disperse dyes that are stable to
pH 9.5 at least
Use the buffer which can
Stabilise the dyes
Provide adequate buffering
Chelate metal ions
Assist dissolution of oligomers

Alkaline buffer for alkaline

dyeing
Extensive range of amino acid derivatives applied in
combination with an alkali
N,N-bis(hydroxyethyl)glycine in combination with sodium
hydroxide

N,N-bis(hydroxyethyl)glycine

N,N-dimethylglycine, N-methylglycine and Nmethylalanine are also listed as preferred compounds

Sequestering agent and important

factors for selection
Sequestering power.
Ability for removal or the neutralizing of harmful metal ions
(water hardening substances, heavy metal ions) from the
water.

Complex stability constant.

Equilibrium constant of COMPLEX : FREE LIGAND.

Dispersibility.
Ability to distributed the solid particle in liquid.

Buffer capacity.
Maintain the pH of solution as narrow or constant.

Typical of sequestering agent

for disperse dyeing
Aminopolycarboxylate
Advantages:
High selectivity for heavy metal ions
Good stability at increased temperatures
Good alkali resistance.

Organic phosphonate
Advantages:
High calcium, magnesium and iron binding capacity
Very selective effect on polyvalent heavy metal ions
Effective in the lower stoichiometric region.

Electrolyte
Unnecessary for the application of
disperse dyes alone.
High concentration of salt often used with
reactive dyes can have an adverse effect
on dispersion stability.
Electrolyte-stable formulations of
disperse dyes or auxiliaries should be
selected.

Levelling agents
Dispersing agents
Promote level dyeing by control of exhaustion during the
heating phase of dyeing
Higher concentrations have a greater retarding effect.
Few promote dye migration.

Levelling agents
Tend to solubilise the dye much more effectively
Contribute to level dyeing both by a retarding effect and
through the promotion of migration.
Generally more powerful levelling effects.

Levelling agent
Non-ionic levelling agent tend to be separated at high
temperature but can increase dyes solubilisation (Low
cloud point)
Anionic levelling agent can increase the cloud point of
nonionic agent
Should synergistic mixing together
7-10% of B in A can increase cloud point of A alone
(105oC) to 150oC
Fully effective at pH >7 (Carefully selection of dyes)

(A) fatty acid ethoxylate

(B) sodiumdodecylbenzenesulphonate

Levelling agent for disperse dyes

Modified nonionic (or Modified anionic,
Weakly anionic)
Phosphate ester ethoxylation

High temperature stability

Protect hardness and trace metal ion
Stabilise under high concentration of electrolyte
Fully effective at pH 4-5 (pH of disperse dyeing)

Levelling agent for disperse dyes

Oligo-soaps or Ethoxylated multi-ester
compounds.

More stable dye dispersion at high temperature

Solubilisation take place at a lower temperature
Dyeing rate at lower temp. is much slower
Solubilisation of oligomer and acrylic size
Low foaming

Carriers
Although polyester fibres are normally
dyed at high temperatures, their blends
with wool are still dyed at or near the boil.
Qualities of texturised polyester that suffer
loss of crimp at 130 C.

Harmful effects from carrier

dyeing : 3 ways
Residual carrier in the dyebath contributes to
effluent pollution and may be environmentally
harmful
Carrier that is volatilised during dyeing or
subsequent heat setting becomes an
atmospheric contaminant
Residual carrier in the fibre can be a health
hazard, as well as causing an unpleasant odour
on heating or during storage.

Typical and properties of some

carrier based.
o-Phenylphenol, tend to lower the light fastness of many
dyes if carrier residues remain in the dyed fibre.
Chlorobenzenes, have no effect on this property, but
strong odour and are both toxic and difficult to
biodegrade.
Biphenyl is relatively non-toxic to river life but is not
readily biodegradable.
Methylnaphthalene, also of low toxicity, is moderately
biodegradable.
Butyl benzoate are relatively efficient in promoting
migration on PES/WO blends
N-alkylphthalimide have no odour and good efficiency

Dyeing of polyester
Carrier dyeing at near or at boiling
temperature
HT dyeing at 120 140oC
Pad-Thermosol dyeing

Mechanism of disperse dyeing

during process
Temperature

Boiling with carrier/

130oC without carrier

CDT

Diffusion
phase

Migration
phase
CDT ; Critical dyeing temperature
Range of 80 120oC

Relaxation
phase

Time

Troubleshooting during dyeing

Disperse dye reduction in the dyebath
Disperse dye hydrolysis in the
dyebath

Disperse dye reduction in the

dyebath:

The amines resulting from A and B do not dye polyester, or only dye it a
weak yellowish shade.

Unfavourable conditions of
reduction of disperse azo dyes
Blend fibres
containing
reducing
groups

auxiliaries
to solubilise
the dye too
much

pH > 6

slower
dyeing
Risk for dyes

Reducing
metal ions
(Cu+, Fe++)

High
density
fiber

anaerobic
dyeing
conditions
Phenolic
dispersing
agents

Disperse dye hydrolysis in the

dyebath.

A: The hydrolysed dye gives bluer red dyeings than the esterified on polyester.
B: The hydrolyzed dye dyes polyester only a little.

How to solve?
Reduction during dyeing
Remove trace metal ion (Sequestering agent)
Replace the lignosulphonate/napthalene
sulphonate with others (Levelling agent)
Accelerate to the appropriate dyeing rate (Carrier
or Accelerating agent)

Hydrolysation during dyeing

Control to acidic pH range (pH controller)
Accelerate to the appropriate dyeing rate (Carrier
or Accelerating agent)

Reduction clearing
Reducing agent with appropriate condition
Alkaline condition
Hydros stabilise (conventional)
Thiourea dioxide

Acidic condition
Reducing agent with acidic pH (formulated reducing agent) e.g.
sulphinic acid derivative with suitable catalyst

No pH changes needed,
Low COD, high biodegradability, low toxicity,
Savings of time and water consumption
Washing fastness as the hydros/caustic soda for disperse azo dyes.
But not for anthraquinone or other chemical type.
Temperature should not > 70oC (higher than wet-Tg of

polyester)
Surfactant can increase the efficiency of reduction
clearing.

Reduction clearing of Disperse azo

dyes

Example
Cl

Cl
CH3
O2N

N N

CH3

4H

NH2 + H2N

O2N

CH2CH2OH

CH2CH2OH
Cl

CI Disperse Orange 5

Cl

Reducing agent :
Fastness of black polyester dyeings after various reduction clearing
treatments

Moisture management of polyester

(PES)
Hydrophobic interaction with oil.
Electric static force provide the soil and
uncomfortable wearing.
Chemical should provide the hydrophilicity
on the fiber surface.

Schematic of Short chain

hydrophilic polyester action on PES

Typical short chain hydrophilic

polyester

> 51,000 Patents

Very complex area

Detergency with & without a soil

release polymer (SRP)

Thermomigration
Degree of thermomigration depend on structure
of a dye, MW, diffusion coefficient or fastness to
sublimation.
Temperature has a greater effect than time in
promoting thermomigration.
Silicone softener and hydrophilic polyester can
increase thermomigration.
The application by padding of an organotin
catalyst along with any other finishing agents
gives rise to a reducing effect during subsequent
dry heat treatment.

Cause of wash fastness

problems on polyester
dyeing

Polyester fiber

Reduction
clear

Heat set/
Chemical finish

Dye on fiber surface

Consumer
washing
Staining on white adjacent

Pressing/
storage

Colour change after heat setting

of incompatible dyes
Yellow migrate to surface

Blue migrate to inside

Heat setting

Dyeing with blends of

Low diffusion blue/
High diffusion yellow

Greener
Colour change

Conclusion :
Polyester can be dyed with disperse dyes
which can adsorb as the solid solution.
The optimum dyeing conditions of
disperse dyes are depend on the disperse
dyes type and fabric type.
The quality of water and careful auxiliaries
selection is the important parameter for
reproducibility.