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 Cotton Wool Regenerated cellulose (staple and filament) Polyester (staple and filament) Nylon (staple and filament) Polypropylene (staple and filament) Acrylic total 1980 47 5.4 11.5 18.0 9.9 1.5 6.8 100 1990 47 4.2 8.1 22.0 9.6 3.0 5.8 100 2000 (est) 40 2.6 4.8 34.0 7.3 6.0 5.0 100 2010 (est) 31 2.0 4.1 39.5 6.6 12.0 4.6 100

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 Orange Red Pink Violet Blue Black Nitrodiphenylamine ; Heterocyclic ; Azo with pyridone coupler Azo Azo; Anthraquinone ; Benzodifuranone Anthraquinone ; Benzodifuranone Azo; Anthraquinone Azo; Anthraquinone ; Thiophene 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 Hydrochloric acid HCl Sulphuric acid H2SO4 Formic acid HCOOH Lactic acid C3H6O3 Acetic acid CH3COOH g/l pH g/l pH g/l pH g/l pH g/l pH

pH value of some common acid in distilled water.

2N 92.0 1.61 180.0 1.78 120.0 2.18

1N 36.5 0.11 49.0 0.24 46.0 1.79 90.0 1.97 60.0 2.40

0.1 N 3.65 1.08 4.9 1.17 4.60 2.32 9.00 2.43 6.00 2.87

xN 1 g/l 1.61 1 g/l 1.79 1 g/l 2.76 1 g/l 2.94 1 g/l 3.27

0.01 N 0.37 2.00 0.49 2.05 0.46 2.85 0.90 2.95 0.60 3.37

0.001 N 0.037 3.00 0.049 3.00 0.046 3.42 0.090 3.50 0.060 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 Reducing metal ions (Cu+, Fe++) Risk for dyes anaerobic dyeing conditions Phenolic dispersing agents

High density fiber

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
l H O H l H OH l H O H +H H H OH l H

CI Disperse Orange 5

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 Reduction clear

Polyester fiber

Dye on fiber surface

Heat set/ Chemical finish

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.