10th June 2006 Indian Institute of Technology

Developments in Developments in Dyeing of PolyesterDyeing of PolyesterDevelopments in Developments in

Dyeing of PolyesterDyeing of Polyester

M.L. GulrajaniM.L. GulrajaniM.L. GulrajaniM.L. Gulrajani

Main ComponentsMain Components

1. Disperse Dye1. Disperse Dye 1. Disperse Dye1. Disperse Dye

2. Specialty Chemicals2. Specialty Chemicals 2. Specialty Chemicals2. Specialty Chemicals

3. Dyeing Procedures3. Dyeing Procedures 3. Dyeing Procedures3. Dyeing Procedures

4. Dyeing Machines4. Dyeing Machines 4. Dyeing Machines4. Dyeing Machines

Disperse DyesDisperse Dyes

1. Modification of Cellulose Acetate Dyes1. Modification of Cellulose Acetate Dyes1. Modification of Cellulose Acetate Dyes1. Modification of Cellulose Acetate Dyes

2. Dyes Developed for Polyester2. Dyes Developed for Polyester 2. Dyes Developed for Polyester2. Dyes Developed for Polyester

3. Rapid Dyeing Dyes – For On-tone Dyeing3. Rapid Dyeing Dyes – For On-tone Dyeing3. Rapid Dyeing Dyes – For On-tone Dyeing3. Rapid Dyeing Dyes – For On-tone Dyeing

4. Dyes for Automotive Fabrics > Light Fastness4. Dyes for Automotive Fabrics > Light Fastness4. Dyes for Automotive Fabrics > Light Fastness4. Dyes for Automotive Fabrics > Light Fastness

5. Dyes for Sports Wear – High Wash Fastness5. Dyes for Sports Wear – High Wash Fastness 5. Dyes for Sports Wear – High Wash Fastness5. Dyes for Sports Wear – High Wash Fastness 6. High Visibility Dyes – Fluorescent Dyes6. High Visibility Dyes – Fluorescent Dyes6. High Visibility Dyes – Fluorescent Dyes6. High Visibility Dyes – Fluorescent Dyes

7. Dyes for Other Specific Applications7. Dyes for Other Specific Applications7. Dyes for Other Specific Applications7. Dyes for Other Specific Applications

Modification of Cellulose Acetate DyesModification of Cellulose Acetate Dyes

C.I. Disperse Violet 1

C.I. Disperse Violet 27

Low Gas Fume Fading Fastness

Dyes Developed for PolyesterDyes Developed for Polyester

Terasil WW polyester dyes Terasil WW polyester dyes incorporate benzodifuranone incorporate benzodifuranone

First Benzodifufuranone DyeFirst Benzodifufuranone DyeFirst Benzodifufuranone DyeFirst Benzodifufuranone Dye

1990199019901990Dispersol PC DyeDispersol PC Dye

Azobenzo - Thiophene DyeAzobenzo - Thiophene Dye

Rapid Dyeing DyesRapid Dyeing Dyes

CompatibilityCompatibility

Dip Test – Du Pont- 1975Dip Test – Du Pont- 1975

V- number – YCL – 1976V- number – YCL – 1976

V = 70 – tV = 70 – t1/21/2/10/10

Serilene V DyesSerilene V Dyes

Mitsui’s V – number - 1977Mitsui’s V – number - 1977

V = 70/(Te – Ts)/HV = 70/(Te – Ts)/H

Miketon Polyester R-PEF DyesMiketon Polyester R-PEF Dyes

Foron RD Dyes – SandozForon RD Dyes – Sandoz

Sumikaron E - RPD DyesSumikaron E - RPD Dyes

Compatible Trichromatic DyesCompatible Trichromatic Dyes

C.I. Disperse Yellow 54C.I. Disperse Yellow 54C.I. Disperse Red 60C.I. Disperse Red 60C.I. Disperse Blue 56C.I. Disperse Blue 56

C.I. Disperse Orange 29C.I. Disperse Orange 29C.I. Disperse Red 60C.I. Disperse Red 60C.I. Disperse Blue 56C.I. Disperse Blue 56C.I. Disperse Violet 33C.I. Disperse Violet 33

Dianix AC-E Dyes – MitsubishiDianix AC-E Dyes – MitsubishiCompact System – ICICompact System – ICIC.I. Disperse Red 60C.I. Disperse Red 60C.I. Disperse Blue 56C.I. Disperse Blue 563-4 medium energy dyes3-4 medium energy dyes

Rapid Dyeing DyesRapid Dyeing Dyes

Dyes for Automotive FabricsDyes for Automotive Fabrics

Disperse Red 60 Disperse Blue 27

Disperse Red 167:1 Disperse Yellow 86

AQ red and blue dyes having AQ red and blue dyes having –OH group at –OH group at -position to -position to the carbonyl group has the the carbonyl group has the ability to undergo intra-ability to undergo intra-molecular proton transfer molecular proton transfer followed by absorption in UV followed by absorption in UV region. Through this internal region. Through this internal conversion process the UV conversion process the UV energy is dissipatedenergy is dissipated

Intra-molecular hydrogen bonding

Proton transfer leads to UV stabilization

Dyes for SportswearDyes for Sportswear

Coralene XFCoralene XF

TERASIL® WWTERASIL® WW Benzodifufuranone DyeBenzodifufuranone Dye

Dyes with High Dyes with High Wash FastnessWash Fastness

High Visibility DyesHigh Visibility Dyes EN471:2003

Some workers who may use Some workers who may use high visibility clothing are:high visibility clothing are:

Traffic controllers Traffic controllers

Train shunters Train shunters

Crane chasers Crane chasers

Track workers Track workers

Road workers Road workers

Ground crews Ground crews

Emergency service Emergency service personnel personnel Coumarin DerivativesCoumarin Derivatives

Dianix Luminous, Coralene Lumin.Dianix Luminous, Coralene Lumin.

Dyes for Specific ApplicationsDyes for Specific Applications

Dybln Scarlet GDybln Scarlet G

Dyes for Transfer PrintingDyes for Transfer Printing

Dyes for Dyeing from Alkaline BathDyes for Dyeing from Alkaline Bath

Dyes for SCFE DyeingDyes for SCFE Dyeing

Dyes for Solvent DyeingDyes for Solvent Dyeing

Dyes for Ink Jet PrintingDyes for Ink Jet Printing

Dyes for Dybln ProcessDyes for Dybln Process

Dyes for Transfer PrintingDyes for Transfer Printing

Black GLM

Blue 2RP

Blue RP

Blue BL

Blue BR

Turquoise Blue BP

Red BB

Red 2BP

Pink GP

Orange L2G

Yellow 7GP

1 : 81 : 4Crude

Ratio

Product Name

Alkali Stability of Disperse DyesAlkali Stability of Disperse Dyes

Non-stableNon-stableNon-stableNon-stable

StableStableStableStable StableStableStableStable

C.

I. D

isp

ers

e

C.

I. D

isp

ers

e

Yello

w 7

7Yello

w 7

7

C. I. Disperse Yellow 58C. I. Disperse Yellow 58

Coralene AS,Coralene AS, Coralene AS,Coralene AS, Dianix® ADDianix® AD Dianix® ADDianix® AD

Dyes for Ink Jet PrintingDyes for Ink Jet Printing

Three ink requirementsThree ink requirements

1 -Image stability1 -Image stabilityResistant to light, water, Resistant to light, water, sweat, and abrasionsweat, and abrasion

2 -Safety2 -SafetyNon-toxic, non-carcinogenicNon-toxic, non-carcinogenic

3 -Storage life of years3 -Storage life of yearsDyes remain dispersedDyes remain dispersed

Three ink requirementsThree ink requirements

1 -Image stability1 -Image stabilityResistant to light, water, Resistant to light, water, sweat, and abrasionsweat, and abrasion

2 -Safety2 -SafetyNon-toxic, non-carcinogenicNon-toxic, non-carcinogenic

3 -Storage life of years3 -Storage life of yearsDyes remain dispersedDyes remain dispersed

Specialty ChemicalsSpecialty Chemicals

1. Dispersing Agents1. Dispersing Agents1. Dispersing Agents1. Dispersing Agents

2. Leveling Agent2. Leveling Agent2. Leveling Agent2. Leveling Agent

3. Colour Yield Improving Agent 3. Colour Yield Improving Agent 3. Colour Yield Improving Agent 3. Colour Yield Improving Agent

4. Oligomer controlling Agent4. Oligomer controlling Agent4. Oligomer controlling Agent4. Oligomer controlling Agent

5. Antifoaming Agent5. Antifoaming Agent5. Antifoaming Agent5. Antifoaming Agent

6. pH Controlling Agent6. pH Controlling Agent6. pH Controlling Agent6. pH Controlling Agent

Dispersing AgentsDispersing AgentsLignin SulphonatesLignin Sulphonates

Oligocondensate of Naphthalene Oligocondensate of Naphthalene Sulphonic acidSulphonic acid

Micelles of Dispersing AgentMicelles of Dispersing Agent

Micelle Assemblies of Anionic Dispersing AgentsMicelle Assemblies of Anionic Dispersing AgentsMicelle Assemblies of Anionic Dispersing AgentsMicelle Assemblies of Anionic Dispersing Agents

Dye DispersionDye Dispersion

Dye Aggregate

Dye Molecules

Anionic Dispersing Agent

Dye Molecules in Surfactant Micelles

Calix ([4]) risorcinarenesCalix ([4]) risorcinarenes

(Four alkyl chains)(Four alkyl chains)

Dialkyldimethylammonium bromide Dialkyldimethylammonium bromide (DADMAB)(DADMAB)

(Two alkyl chains)(Two alkyl chains)

Dispersing AgentsDispersing Agents

Dispersing AgentsDispersing Agents

Propanediyl-α,ω-bis (dimethyldodecylammonium Propanediyl-α,ω-bis (dimethyldodecylammonium bromide)bromide)

Hexanediyl-α,ω-bis (dimethyldodecylammonium Hexanediyl-α,ω-bis (dimethyldodecylammonium bromidebromide

Gemini SurfactantsGemini SurfactantsGemini surfactants possess at least two hydrophobic chains and two Gemini surfactants possess at least two hydrophobic chains and two

ionic or polar groupsionic or polar groups

Surfactant BilayersSurfactant Bilayers

AggregationAggregation

in waterin water

WaterWater

WaterWater

30 A30 A

Aqueous Aqueous interiorinterior

Aqueous exteriorAqueous exterior

Surfactant with two alkyl chainsSurfactant with two alkyl chains

Dyes Dissolved in BilayerDyes Dissolved in Bilayer

Entrap dyes inside a Entrap dyes inside a vesiclevesicle

Deliver dyes to the Deliver dyes to the desired areadesired area

Release dyes at the Release dyes at the target areatarget area

Dye MoleculesDye Molecules

Dyeing ProceduresDyeing Procedures Rapid Dyeing ProcessesRapid Dyeing Processes

Suproma – Sandoz -1969Suproma – Sandoz -1969 Resolin S – Bayer – 1970Resolin S – Bayer – 1970 Palegal Process – BASF – 1973Palegal Process – BASF – 1973 Desk – KP System – Nippon Kayaku – 1975Desk – KP System – Nippon Kayaku – 1975 Mitsui’s MRD Process – 1977Mitsui’s MRD Process – 1977 Sodyeco & Comodye System – 1979Sodyeco & Comodye System – 1979 Compact System – ICI - 980Compact System – ICI - 980 Palanil High Speed System –1983Palanil High Speed System –1983Classical Optimisation SystemsClassical Optimisation SystemsThese systems were computerisedThese systems were computerisedIsothermal Dyeing System – Rapid Color Process - HoechstIsothermal Dyeing System – Rapid Color Process - Hoechst

Blind DyeingBlind Dyeing

Dyeing ProceduresDyeing Procedures

606000CC

808000CC

13013000CC

00 35-4035-40 100-160100-160

Sorption Sorption StageStage

Diffusion Diffusion and and

Migration Migration StageStage

Cooling Cooling StageStage

1.5

– 2.

0

1.5

– 2.

000 C

/min

C/m

in

Dyeing Time (min)Dyeing Time (min)

CONVENTIOAL DYEING CYCLECONVENTIOAL DYEING CYCLE

606000CC

85-10085-10000CC

115-130115-13000CC

13013000CC

VcVcHmHm

TsTs TTEE

DDSorption Sorption StageStage

Cooling Cooling StageStage

Diffusion Diffusion StageStage

RAPID DYEING CYCLERAPID DYEING CYCLE

Software : Optidye P of DyeStar for Dianex CC dyesSoftware : Optidye P of DyeStar for Dianex CC dyes

Temporarily Solubilised Disperse DyesTemporarily Solubilised Disperse Dyes

No substantivity, No substantivity, SolubleSoluble

Substantive, Substantive, InsolubleInsolubleReactiveReactive

Less substantive, Less substantive, HydrolysedHydrolysed

Temporarily solubilised Temporarily solubilised

disperse dyes derived disperse dyes derived

from aminophenyl-4-(b-from aminophenyl-4-(b-

sulphatoethylsulphone) sulphatoethylsulphone)

are exhausted on the are exhausted on the

polyester fibre mostly in polyester fibre mostly in

the vinylsulphone form the vinylsulphone form

and to a lesser extent as and to a lesser extent as

theirtheir

hydroxyethylsulphone hydroxyethylsulphone

analogues.analogues.

Aftertreatment of polyester fabric dyed with temporarily solubilised disperse dyes, W J Lee and J P Kim, JSDC,116 (2000) 345

Dyeing Polyester with Microencapsulated Disperse DyesDyeing Polyester with Microencapsulated Disperse Dyes

Dyeing polyester with microencapsulated disperse dyes in the absences of auxiliaries, Zhong Yi, et al., Color. Technology, 121 (2005) 76Dyeing polyester with microencapsulated disperse dyes in the absences of auxiliaries, Zhong Yi, et al., Color. Technology, 121 (2005) 76

Polyurea microcapsules Polyurea microcapsules

prepared by using disperse prepared by using disperse

dyes as core material and dyes as core material and

diphenlmethane -4,4’ diphenlmethane -4,4’

diisocyanate as wall material diisocyanate as wall material

when dyed on polyester at when dyed on polyester at

high temperature completely high temperature completely

exhaust in the absence of exhaust in the absence of

auxiliary chemicals such as auxiliary chemicals such as

dispersants etc. hence this dispersants etc. hence this

method is considered as an method is considered as an

eco-friendly methodeco-friendly method

SCFE DyeingSCFE DyeingSupercritical carbon dioxide is an Supercritical carbon dioxide is an alternative dyeing technology that alternative dyeing technology that eliminates the use of water while eliminates the use of water while achieving results comparable to current achieving results comparable to current dyeing processes. Supercritical COdyeing processes. Supercritical CO22 is is harmless ecologically, available, non-harmless ecologically, available, non-toxic and nonexplosive. When placed toxic and nonexplosive. When placed above the critical point (31.1°C and 73 above the critical point (31.1°C and 73 atm) COatm) CO22 becomes a remarkable becomes a remarkable solvent for many natural and synthetic solvent for many natural and synthetic dyes. The dye solution in the dyes. The dye solution in the supercritical COsupercritical CO22 is carried to the fiber is carried to the fiber to be dyed. Under certain conditions, to be dyed. Under certain conditions, the gas-like diffusion of supercritical the gas-like diffusion of supercritical COCO22 disperses the dye evenly into the disperses the dye evenly into the small pores and crevices of the fiber.small pores and crevices of the fiber.

Dyeing ConditionsDyeing Conditions

Extraction vessel: 40 LiterExtraction vessel: 40 Liter

Fiber: 4 PET PackagesFiber: 4 PET Packages

Dye: C.1. Disperse Blue 79Dye: C.1. Disperse Blue 79

Pressure: 4200 psiPressure: 4200 psi

Temperature: 120ºCTemperature: 120ºC

CO2 Recirculation: 5 Kgs/minCO2 Recirculation: 5 Kgs/min

Dye time: 40 minutesDye time: 40 minutes

Dyeing with IndigoDyeing with Indigo

Insoluble PigmentInsoluble Pigment Alkaline Lecuo VatAlkaline Lecuo Vat(Soluble)(Soluble)

Vat AcidVat Acid(Sparingly Soluble)(Sparingly Soluble)

Indigo adsorption properties to polyester fibers of different levels of fineness, Young-A. S et al., Dyes and Pigments 65 (2005) 137Indigo adsorption properties to polyester fibers of different levels of fineness, Young-A. S et al., Dyes and Pigments 65 (2005) 137

Hydrogen bondingHydrogen bonding

Hydrogen bondingHydrogen bonding

Solubilising effectSolubilising effect Swelling effectSwelling effect

UREAUREA

Dyeing MachinesDyeing Machines

VENTRURAVENTRURA

Dyeing MachinesDyeing Machines

Dyeing MachinesDyeing Machines

WHO SAYS IT IS DIFFICULT TO WHO SAYS IT IS DIFFICULT TO DYE POLYESTER DYE POLYESTER

WHO SAYS IT IS DIFFICULT TO WHO SAYS IT IS DIFFICULT TO DYE POLYESTER DYE POLYESTER

Thank youThank youThank youThank you